Photochromic materials having extended pi-conjugated systems and compositions and articles including the same

ABSTRACT

The present invention provides a photochromic material which is an indeno-fused naphthopyran having a pi-conjugation extending group bonded to the 11-position of the indeno-fused naphthopyran, the pi-conjugation extending group having at least one pendent halo-substituted group bonded thereto. The pi-conjugation extending group extends the pi-conjugation system of said indeno-fused naphthopyran. The 13-position of the indeno-fused naphthopyran is substantially free of spiro-substituents. The invention further provides photochromic materials of specified structure, photochromic compositions, photochromic articles and optical elements that include the photochromic material.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.12/136,339, filed Jun. 10, 2008, which is a division of U.S. patentapplication Ser. No. 11/102,279, filed Apr. 8, 2005, each of which isincorporated by reference herein in its entirety. The inventions claimedin this application were made as a result of activities undertakenwithin the scope of a joint research agreement between TransitionsOptical, Inc. and Johnson & Johnson Vision Care, Inc. having aneffective date of Apr. 1, 2003.

BACKGROUND

Various non-limiting embodiments disclosed herein relate to photochromicmaterials having an extended pi-conjugated system. Other non-limitingembodiments relate to photochromic compositions and articles, such asoptical elements, incorporating the same.

Many conventional photochromic materials, such as indeno-fusednaphthopyrans, can undergo a transformation in response to certainwavelengths of electromagnetic radiation (or “actinic radiation”) fromone form (or state) to another, with each form having a characteristicabsorption spectrum. As used herein the term “actinic radiation” refersto electromagnetic radiation that is capable of causing a photochromicmaterial to transform from one form or state to another. For example,many conventional photochromic materials are capable of transformingfrom a closed-form, corresponding to a “bleached” or “unactivated” stateof the photochromic material, to an open-form, corresponding to a“colored” or “activated” state of the photochromic material, in responseto actinic radiation, and reverting back to the closed-form in theabsence of the actinic radiation in response to thermal energy.Photochromic compositions and articles that contain one or morephotochromic materials, for example photochromic lenses for eyewearapplications, may display clear and colored states that generallycorrespond to the states of the photochromic material(s) that theycontain.

Typically, the amount of a photochromic material needed to achieve adesired optical effect when incorporated into a composition or articlewill depend, in part, on the amount of actinic radiation that thephotochromic material absorbs on a per molecule basis. That is, the moreactinic radiation that the photochromic material absorbs on a permolecule basis, the more likely (i.e., the higher the probability) thephotochromic material will transform from the closed-form to theopen-form. Photochromic compositions and articles that are made usingphotochromic materials having a relatively high molar absorptioncoefficient (or “extinction coefficient”) for actinic radiation maygenerally be used in lower concentrations than photochromic materialshaving lower molar absorption coefficients, while still achieving thedesired optical effect.

For some applications, the amount of photochromic material that can beincorporated into the article may be limited due to the physicaldimensions of the article. Accordingly, the use of conventionalphotochromic materials that have a relatively low molar absorptioncoefficient in such articles may be impractical because the amountphotochromic material needed to achieve the desired optical effectscannot be physically accommodated in the article. Further, in otherapplications, the size or solubility of the photochromic material itselfmay limit the amount of the photochromic material that can beincorporated into the article. Additionally, since photochromicmaterials may be expensive, in still other applications, the amount ofphotochromic material be used may be limited due to economicconsiderations.

Accordingly, for some applications, it may be advantageous to developphotochromic materials that can display hyperchromic absorption ofactinic radiation, which may enable the use of lower concentrations ofthe photochromic material while still achieving the desired opticaleffects. As used herein, the term “hyperchromic absorption” refers to anincrease in the absorption of electromagnetic radiation by aphotochromic material having an extended pi-conjugated system on a permolecule basis as compared to a comparable photochromic material thatdoes not have an extended pi-conjugated system.

Additionally, as mentioned above, typically the transformation betweenthe closed-form and the open-form requires that the photochromicmaterial be exposed to certain wavelengths of electromagnetic radiation.For many conventional photochromic materials, the wavelengths ofelectromagnetic radiation that may cause this transformation typicallyrange from 320 nanometers (“nm”) to 390 nm. Accordingly, conventionalphotochromic materials may not be optimal for use in applications thatare shielded from a substantial amount of electromagnetic radiation inthe range of 320 nm to 390 nm. For example, lenses for eyewearapplications that are made using conventional photochromic materials maynot reach their fully-colored state when used in an automobile. This isbecause a large portion of electromagnetic radiation in the range of 320nm to 390 nm can be absorbed by the windshield of the automobile beforeit can be absorbed by the photochromic material(s) in the lenses.Therefore, for some applications, it may be advantageous to developphotochromic materials that can have a closed-form absorption spectrumfor electromagnetic radiation that is shifted to longer wavelengths,that is “bathochromically shifted.” As used herein the term “closed-formabsorption spectrum” refers to the absorption spectrum of thephotochromic material in the closed-form or unactivated state. Forexample, in applications involving behind the windshield use ofphotochromic materials, it may be advantageous if the closed-formabsorption spectrum of the photochromic material were shifted such thatthe photochromic material may absorb sufficient electromagneticradiation having a wavelength greater than 390 nm to permit thephotochromic material to transform from the closed-form to an open-form.

BRIEF SUMMARY OF THE INVENTION

The present invention is directed to a photochromic material comprisingan indeno-fused naphthopyran comprising a pi-conjugation extending groupbonded to the 11-position of the indeno-fused naphthopyran, wherein thepi-conjugation extending group extends the pi-conjugation system of theindeno-fused naphthopyran. The pi-conjugation extending group has atleast one pendent halo-substituted group bonded thereto, and the13-position of the indeno-fused naphthopyran is substantially free ofspiro-substituents.

The present invention further provides a photochromic materialrepresented by graphic formulas I and II:

or a mixture thereof, wherein substituent groups R^(a), R^(b), R^(c),R^(d), R^(e), B, and B′, and m and n are as described herein below inthe claims.

Also provided is a photochromic composition comprising the photochromicmaterial described above incorporated into at least a portion of anorganic material comprised of a polymeric material, an oligomericmaterial, a monomeric material or a mixture or combination thereof.

The present invention also is directed to a photochromic article and anoptical element comprising the above-described photochromic material.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a representative schematic diagram of a reaction scheme formaking an intermediate material that may be used in forming photochromicmaterials according to the present invention;

FIGS. 2 through 5 are representative schematic diagrams of reactionschemes that may be used in making photochromic materials according tothe present invention;

FIG. 6 is a representative general chemical formula of an indeno-fusednaphthopyran according to the present invention;

FIG. 7 is a representative general chemical formula of an indeno-fusednaphthopyran according to the present invention; and

FIG. 8 is a representative general chemical formula of an indeno-fusednaphthopyran according to the present invention.

DETAILED DESCRIPTION

As used in this specification and the appended claims, the articles “a,”“an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

Additionally, for the purposes of this specification, unless otherwiseindicated, all numbers expressing quantities of ingredients, reactionconditions, and other properties or parameters used in the specificationare to be understood as being modified in all instances by the term“about.” Accordingly, unless otherwise indicated, it should beunderstood that the numerical parameters set forth in the followingspecification and attached claims are approximations. At the very least,and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims, numerical parameters should beread in light of the number of reported significant digits and theapplication of ordinary rounding techniques.

Further, while the numerical ranges and parameters setting forth thebroad scope of the invention are approximations as discussed above, thenumerical values set forth in the Examples section are reported asprecisely as possible. It should be understood, however, that suchnumerical values inherently contain certain errors resulting from themeasurement equipment and/or measurement technique.

Photochromic materials according to various non-limiting embodiments ofthe invention will now be discussed. As used herein, the term“photochromic” means having an absorption spectrum for at least visibleradiation that varies in response to absorption of at least actinicradiation. Further, as used herein the term “photochromic material”means any substance that is adapted to display photochromic properties,i.e. adapted to have an absorption spectrum for at least visibleradiation that varies in response to absorption of at least actinicradiation. As previously discussed, as used herein the term “actinicradiation” refers to electromagnetic radiation that is capable ofcausing a photochromic material transform from one form or state toanother.

As previously mentioned, the present invention is directed to aphotochromic material comprising an indeno-fused naphthopyran comprisinga pi-conjugation extending group bonded to the 11-position of theindeno-fused naphthopyran, the pi-conjugation extending group having atleast one pendent halo-substituted group bonded thereto. Thepi-conjugation extending group serves to extend the pi-conjugationsystem of the indeno-fused naphthopyran. The 13-position of theindeno-fused naphthopyran is substantially free of spiro-substituents.

As used herein, the terms “10-position,” “11-position,” “12-position,”“13-position,” etc. refer to the 10-, 11-, 12- and 13-position, etc. ofthe ring atoms of the indeno-fused naphthopyran, respectively. Forexample, according to one non-limiting embodiment wherein theindeno-fused naphthopyran is an indeno[2′,3′:3,4]naphtho[1,2-b]pyran,the ring atoms of the indeno-fused naphthopyran are numbered as shownbelow in (I). According to another non-limiting embodiment wherein theindeno-fused naphthopyran is an indeno[1′,2′:4,3]naphtho[2,1-b]pyran,the ring atoms of the indeno-fused naphthopyran are numbered shown belowin (II).

Further, according to various non-limiting embodiments disclosed herein,the indeno-fused naphthopyrans may have group(s) that can stabilize theopen-form of the indeno-fused naphthopyran bonded to the pyran ring atan available position adjacent the oxygen atom (i.e., the 3-position in(I) above, or the 2-position in (II) above). For example, according toone non-limiting embodiment, the indeno-fused naphthopyrans may have agroup that can extend the pi-conjugated system of the open-form of theindeno-fused naphthopyran bonded to the pyran ring adjacent the oxygenatom. Non-limiting examples of groups that may be bonded to the pyranring as discussed above are described in more detail herein below withreference to B and B′.

Further, as discussed in more detail herein below, in addition to thegroup that extends the pi-conjugated system of the indeno-fusednaphthopyran bonded at the 11-position of the indeno-fused naphthopyran,the photochromic materials according to various non-limiting embodimentsdisclosed may include additional groups bonded or fused at variouspositions on the indeno-fused naphthopyran other than the 11-position,provided that the 13-position of the indeno-fused naphthopyran issubstantially free of spiro-substituents.

As used herein, the terms “group” or “groups” mean an arrangement of oneor more atoms. As used herein, the phrase “group that extends thepi-conjugated system of the indeno-fused naphthopyran” means a grouphaving at least one pi-bond (π-bond) in conjugation with thepi-conjugated system of the indeno-fused naphthopyran. It will beappreciated by those skilled in the art that in such system, thepi-electrons in the pi-conjugated system of the indeno-fusednaphthopyran can be de-localized over the pi-system of the indeno-fusednaphthopyran and the group having at least one pi-bond in conjugationwith the pi-conjugated system of the indeno-fused naphthopyran.Conjugated bond systems may be represented by an arrangement of at leasttwo double or triple bonds separated by one single bond, that is asystem containing alternating double (or triple) bonds and single bonds,wherein the system contains at least two double (or triple) bonds.Non-limiting examples of groups that may extend the pi-conjugated systemof the indeno-fused naphthopyran according to various non-limitingembodiments disclosed herein are set forth below in detail.

As previously discussed, the more actinic radiation that a photochromicmaterial absorbs on a per molecule basis, the more likely thephotochromic material will be to make the transformation from theclosed-form to the open-form. Further, as previously discussed,photochromic materials that absorb more actinic radiation on a permolecule basis may generally be used in lower concentrations than thosethat absorb less actinic radiation on a per molecule basis, while stillachieving the desired optical effects.

Although not meant to be limiting herein, it has been observed by theinventors that the indeno-fused naphthopyrans that comprise a group thatextends the pi-conjugated system of the indeno-fused naphthopyran bondedat the 11-position thereof which has at least one pendanthalo-substituted group bonded thereto according to certain non-limitingembodiments of the present invention may absorb more actinic radiationon a per molecule basis than a comparable indeno-fused naphthopyranwithout such a group that extends the pi-conjugated system of thecomparable indeno-fused naphthopyran bonded at the 11-position thereof.That is, the indeno-fused naphthopyrans according to the presentinvention may display hyperchromic absorption of actinic radiation. Asdiscussed above, as used herein the term “hyperchromic absorption”refers to an increase in the absorption of electromagnetic radiation bya photochromic material having an extended pi-conjugated system on a permolecule basis as compared to a comparable photochromic material thatdoes not have an extended pi-conjugated system. Thus, while not meant tobe limiting herein, it is contemplated that the indeno-fusednaphthopyrans according to certain non-limiting embodiments disclosedherein may be advantageously employed in many applications, includingapplications wherein it may be necessary or desirable to limit theamount of the photochromic material employed.

The amount of radiation absorbed by a material (or the “absorbance” ofthe material) can be determined using a spectrophotometer by exposingthe material to incident radiation having a particular wavelength andintensity and comparing the intensity of radiation transmitted by thematerial to that of the incident radiation. For each wavelength tested,the absorbance (“A”) of the material is given by the following equation:A=log I ₀ /Iwherein “I₀” is the intensity of the incident radiation and “I” is theintensity of the transmitted radiation. An absorption spectrum for thematerial can be obtained by plotting the absorbance of a material vs.wavelength. By comparing the absorption spectrum of photochromicmaterials that were tested under the same conditions, that is using thesame concentration and path length for electromagnetic radiation passingthrough the sample (e.g., the same cell length or sample thickness), anincrease in the absorbance of one of the materials at a given wavelengthcan be seen as an increase in the intensity of the spectral peak forthat material at that wavelength.

Another indication of the amount of radiation a material can absorb isthe extinction coefficient of the material. The extinction coefficient(“ε”) of a material is related to the absorbance of the material by thefollowing equation:ε=A/(c×I)wherein “A” is the absorbance of the material at a particularwavelength, “c” is the concentration of the material in moles per liter(mol/L) and “I” is the path length (or cell thickness) in centimeters.Further, by plotting the extinction coefficient vs. wavelength andintegrating over a range of wavelengths (e.g., =∫ε(λ)dλ) it is possibleto obtain an “integrated extinction coefficient” for the material.Generally speaking, the higher the integrated extinction coefficient ofa material, the more radiation the material will absorb on a permolecule basis.

The photochromic materials according various non-limiting embodimentsdisclosed herein may have an integrated extinction coefficient greaterthan 1.0×10⁶ nm/(mol×cm) or (nm×mol⁻¹×cm⁻¹) as determined by integrationof a plot of extinction coefficient of the photochromic material vs.wavelength over a range of wavelengths ranging from 320 nm to 420 nm,inclusive. Further, the photochromic materials according to variousnon-limiting embodiments disclosed herein may have an integratedextinction coefficient of at least 1.1×10⁶ nm×mol⁻¹×cm⁻¹ or at least1.3×10⁶ nm×mol⁻¹×cm⁻¹ as determined by integration of a plot ofextinction coefficient of the photochromic material vs. wavelength overa range of wavelengths ranging from 320 nm to 420 nm, inclusive. Forexample, according to various non-limiting embodiments, the photochromicmaterial may have an integrated extinction coefficient ranging from1.1×10⁶ to 4.0×10⁶ nm×mol⁻¹×cm⁻¹ (or greater) as determined byintegration of a plot of extinction coefficient of the photochromicmaterial vs. wavelength over a range of wavelengths ranging from 320 nmto 420 nm, inclusive. However, as indicated above, generally speakingthe higher the integrated extinction coefficient of a photochromicmaterial, the more radiation the photochromic material will absorb on aper molecule basis. Accordingly, other non-limiting embodimentsdisclosed herein contemplate photochromic materials having an integratedextinction coefficient greater than 4.0×10⁶ nm×mol⁻¹×cm⁻¹.

As previously discussed, for many conventional photochromic materials,the wavelengths of electromagnetic radiation required to cause thematerial to transformation from a closed-form (or unactivated state) toan open-form (or activated state) may range from 320 nm to 390 nm. Thus,conventional photochromic materials may not achieve their fully-coloredstate when used in applications that are shielded from a substantialamount of electromagnetic radiation in the range of 320 nm to 390 nm.Although not meant to be limiting herein, it has been observed by theinventors that indeno-fused naphthopyrans comprising a group thatextends the pi-conjugated system of the indeno-fused naphthopyran at the11-position thereof according to certain non-limiting embodimentsdisclosed herein may have a closed-form absorption spectrum forelectromagnetic radiation that is bathochromically shifted as comparedto a closed-form absorption spectrum for electromagnetic radiation of acomparable indeno-fused naphthopyran without the group that extends thepi-conjugated system of the comparable indeno-fused naphthopyran bondedat the 11-position thereof. As discussed above, as used herein the term“closed-form absorption spectrum” refers to the absorption spectrum ofthe photochromic material in the closed-form or unactivated state.

In the present invention, the indeno-fused naphthopyran comprises api-conjugation extending group bonded to the 11-position of theindeno-fused naphthopyran wherein the pi-conjugation extending group hasat least one pendent halo-substituted group bonded thereto. Thepi-conjugation extending group can be a group represented by—C(R₃₀)═C(R₃₁)(R₃₂) or —C≡C—R₃₃, wherein R₃₀, R₃₁ and R₃₂ are eachindependently, amino, dialkyl amino, diaryl amino, acyloxy, acylamino, asubstituted or unsubstituted C₁-C₂₀ alkyl, a substituted orunsubstituted C₂-C₂₀ alkenyl, a substituted or unsubstituted C₂-C₂₀alkynyl, halogen, hydrogen, hydroxy, oxygen, a polyol residue, asubstituted or unsubstituted phenoxy, a substituted or unsubstitutedbenzyloxy, a substituted or unsubstituted alkoxy, a substituted orunsubstituted oxyalkoxy, alkylamino, mercapto, alkylthio, a substitutedor unsubstituted aryl, a substituted or unsubstituted heteroaryl, asubstituted or unsubstituted heterocyclic group, provided that at leastone of R₃₀, R₃₁ and R₃₂ is the pendent halo-substituted group, and R₃₃is the pendent halo-substituted group.

Additionally, the pendent halo-substituted group of the pi-conjugationextending group can be selected from halo-substituted(C₁-C₁₀)alkyl,halo-substituted (C₂-C₁₀)alkenyl, halo-substituted(C₂-C₁₀)alkynyl,halo-substituted(C₁-C₁₀)alkoxy and halo-substituted(C₃-C₁₀)cycloalkyl,wherein each halo group of each pendent halo-substituted groupindependently is selected from fluorine, chlorine, bromine or iodine.

In a particular embodiment of the present invention, the pi-conjugationextending group having at least one pendent halo-substituted groupbonded thereto can be selected from substituted or unsubstituted aryl,and substituted or unsubstituted heteroaryl, wherein the substitutedaryl and said substituted heteroaryl are in each case independentlysubstituted with at least one member selected from substituted orunsubstituted alkyl, substituted or unsubstituted alkoxy, substituted orunsubstituted oxyalkoxy, amide, substituted or unsubstituted amino,substituted or unsubstituted aryl, substituted or unsubstitutedheteroaryl, azide, carbonyl, carboxy, ester, ether, halogen, hydroxy,polyol residue, substituted or unsubstituted phenoxy, substituted orunsubstituted benzyloxy, cyano, nitro, sulfonyl, thiol, and substitutedor unsubstituted heterocyclic group. In such an embodiment, if the arylgroup or the heteroaryl group comprises more than one substituent, eachsubstituent may be chosen independent of the others.

The photochromic material as described above displays hyperchromicabsorption of electromagnetic radiation having a wavelength from 320 nmto 420 nm as compared to a comparative photochromic material comprisinga comparable indeno-fused naphthopyran that is substantially free of api-conjugation extending group bonded to the 11-position which has atleast one pendent halo-substituted group bonded thereto.

The present invention also is directed to a photochromic articlecomprising a substrate and any of the previously described photochromicmaterials connected to at least a portion of the substrate. Thesubstrate can comprise a polymeric material and the photochromicmaterial can be incorporated into at least a portion of the polymericmaterial. The photochromic material can be blended with at least aportion of the polymeric material, or the photochromic material can bebonded to at least a portion of the polymeric material, and/or thephotochromic material can be imbibed into at least a portion of thepolymeric material.

Such photochromic articles can include an optical element, for example,an ophthalmic element, a display element, a window, a mirror and aliquid crystal cell element. The ophthalmic element can include at leastone of a corrective lens, a non-corrective lens, a magnifying lens, aprotective lens, a visor, goggles, or a lens for an optical instrument.

Additionally, the present invention is directed to a photochromicmaterial represented by graphic formulas I and II:

or a mixture thereof, wherein:

-   (i) R^(a) is a pi-conjugation extending group bonded to the    11-position of the indeno-fused naphthopyran, said pi-conjugation    extending group having at least one pendent halo-substituted group    bonded thereto, the pi-conjugation extending group extending the    pi-conjugation system of the indeno-fused naphthopyran, provided the    13-position of said indeno-fused naphthopyran is substantially free    of spiro-substituents; wherein said pi-conjugation extending group    is a group represented by —C(R₃₀)═C(R₃₁)(R₃₂) or —C═C—R₃₃, wherein    R₃₀, R₃₁ and R₃₂ are each independently, amino, dialkyl amino,    diaryl amino, acyloxy, acylamino, a substituted or unsubstituted    C₁-C₂₀ alkyl, a substituted or unsubstituted C₂-C₂₀ alkenyl, a    substituted or unsubstituted C₂-C₂₀ alkynyl, halogen, hydrogen,    hydroxy, oxygen, a polyol residue, a substituted or unsubstituted    phenoxy, a substituted or unsubstituted benzyloxy, a substituted or    unsubstituted alkoxy, a substituted or unsubstituted oxyalkoxy,    alkylamino, mercapto, alkylthio, a substituted or unsubstituted    aryl, a substituted or unsubstituted heteroaryl, a substituted or    unsubstituted heterocyclic group, provided that at least one of R₃₀,    R₃₁ and R₃₂ is a pendent halo-substituted group, and R₃₃ is the    pendent halo-substituted group; or    -   the pi-conjugation extending group is selected from a        substituted or unsubstituted aryl; and a substituted or        unsubstituted heteroaryl;-   (ii) n ranges from 0 to 3;-   (iii) m ranges from 0 to 4;-   (iv) each R^(d) and R^(e) is independently chosen for each    occurrence from:    -   a reactive substituent; a compatiblizing substituent; hydrogen;        C₁-C₆ alkyl; halo; C₃-C₇ cycloalkyl; a substituted or        unsubstituted phenyl, said phenyl substituents being C₁-C₆ alkyl        or C₁-C₆ alkoxy; —OR¹⁰ or —OC(═O)R¹⁰ wherein R¹⁰ is S, hydrogen,        amine, C₁-C₆ alkyl, phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl        substituted phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substituted        phenyl(C₁-C₃)alkyl, (C₁-C₆)alkoxy(C₂-C₄)alkyl, C₃-C₇ cycloalkyl        or mono(C₁-C₄)alkyl substituted C₃-C₇ cycloalkyl; a        mono-substituted phenyl, said phenyl having a substituent        located at the para position, the substituent being a        dicarboxylic acid residue or derivative thereof, a diamine        residue or derivative thereof, an amino alcohol residue or        derivative thereof, a polyol residue or derivative thereof,        —(CH₂)—, —(CH₂)_(t)— or —[O—(CH₂)_(t)]_(k)—, wherein t ranges        from 2 to 6, and k ranges from 1 to 50, and wherein the        substituent is connected to an aryl group on another        photochromic material; —N(R¹¹)R¹², wherein R¹¹ and R¹² are each        independently hydrogen, C₁-C₈ alkyl, phenyl, naphthyl, furanyl,        benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,        benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl        and fluorenyl, C₁-C₈ alkylaryl, C₃-C₂₀ cycloalkyl, C₄-C₂₀        bicycloalkyl, C₅-C₂₀ tricycloalkyl or C₁-C₂₀ alkoxyalkyl, or R¹¹        and R¹² come together with the nitrogen atom to form a C₃-C₂₀        hetero-bicycloalkyl ring or a C₄-C₂₀ hetero-tricycloalkyl ring;        a nitrogen containing ring represented by:

-   -   wherein each -M- is independently chosen for each occurrence        from —CH₂—, —CH(R¹³)—, —C(R¹³)₂—, —CH(aryl)-, —C(aryl)₂- and        —C(R¹³)(aryl)-, and -Q- is -M-, —O—, —S—, —S(O)—, —SO₂—, —NH—,        —N(R¹³)— or —N(aryl)-, wherein each R¹³ is independently C₁-C₆        alkyl, each (aryl) is independently phenyl or naphthyl, u ranges        from 1 to 3, and v ranges from 0 to 3, provided that if v is 0,        -Q- is -M-; a group represented by:

-   -   wherein each R¹⁵, R¹⁶ and R¹⁷ is independently hydrogen, C₁-C₆        alkyl, phenyl or naphthyl, or R¹⁵ and R¹⁶ together form a ring        of 5 to 8 carbon atoms, each R¹⁴ is independently C₁-C₆ alkyl,        C₁-C₆ alkoxy, halo, and p ranges from 0 to 3; and a substituted        or unsubstituted C₄-C₁₈ spirobicyclic amine or a substituted or        unsubstituted C₄-C₁₈ spirotricyclic amine, wherein said        substituents are independently aryl, C₁-C₆ alkyl, C₁-C₆ alkoxy        or phenyl(C₁-C₆)alkyl; or

-   an R^(e) group in the 6-position and an R^(e) group in the    7-position together form a group represented by:

-   -   wherein each Z and Z′ is independently oxygen or the group        —NR¹¹— wherein R¹¹, R¹⁴ and R¹⁶ are as set forth above;

-   (v) R^(b) and R^(c) are each independently:    -   a reactive substituent; a compatiblizing substituent; hydrogen;        hydroxy; C₁-C₆ alkyl; C₃-C₇ cycloalkyl; allyl; a substituted or        unsubstituted phenyl or benzyl, wherein each of said phenyl and        benzyl substituents is independently C₁-C₆ alkyl or C₁-C₆        alkoxy; halo; a substituted or unsubstituted amino; —C(O)R⁹        wherein R⁹ is hydrogen, hydroxy, C₁-C₆ alkyl, C₁-C₆ alkoxy, an        unsubstituted, mono- or di-substituted phenyl or naphthyl        wherein each of said substituents is independently C₁-C₆ alkyl        or C₁-C₆ alkoxy, phenoxy, mono- or di-(C₁-C₆)alkyl substituted        phenoxy, mono- or di-(C₁-C₆)alkoxy substituted phenoxy, amino,        mono- or di-(C₁-C₆)alkylamino, phenylamino, mono- or        di-(C₁-C₆)alkyl substituted phenylamino or mono- or        di-(C₁-C₆)alkoxy substituted phenylamino; —OR¹⁸ wherein R¹⁸ is        C₁-C₆ alkyl, phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl substituted        phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substituted phenyl(C_(r)        C₃)alkyl, C₁-C₆ alkoxy(C₂-C₄)alkyl, C₃-C₇ cycloalkyl,        mono(C₁-C₄)alkyl substituted C₃-C₇ cycloalkyl, C₁-C₆ haloalkyl,        allyl or —CH(R¹⁹)T wherein R¹⁹ is hydrogen or C₁-C₃ alkyl, T is        CN, CF₃ or COOR²⁰ wherein R²⁹ is hydrogen or C₁-C₃ alkyl, or        wherein R¹⁸ is —C(═O)U wherein U is hydrogen, C₁-C₆ alkyl, C₁-C₆        alkoxy, an unsubstituted, mono- or di-substituted phenyl or        naphthyl, wherein each of said substituents are independently        C₁-C₆ alkyl or C₁-C₆ alkoxy, phenoxy, mono- or di-(C₁-C₆)alkyl        substituted phenoxy, mono- or di-(C₁-C₆)alkoxy substituted        phenoxy, amino, mono- or di-(C₁-C₆)alkylamino, phenylamino,        mono- or di-(C₁-C₆)alkyl substituted phenylamino or mono- or        di-(C₁-C₆)alkoxy substituted phenylamino; and a mono-substituted        phenyl, said phenyl having a substituent located at the para        position, the substituent being a dicarboxylic acid residue or        derivative thereof, a diamine residue or derivative thereof, an        amino alcohol residue or derivative thereof, a polyol residue or        derivative thereof, —(CH₂)—, —(CH₂)_(t)— or —[O—(CH₂)_(t)]_(k)—,        wherein t ranges from 2 to 6 and k ranges from 1 to 50, and        wherein the substituent is connected to an aryl group on another        photochromic material; or    -   R^(b) and R^(c) together form an oxo group; provided that the        13-position of said indeno-fused naphthopyran is substantially        free of spiro-substituents; and

-   (vi) B and B′ are each independently:    -   an aryl group that is mono-substituted with a reactive        substituent or a compatiblizing substituent; an unsubstituted,        mono-, di-, tri- or tetra-substituted aryl group; 9-julolidinyl;        an unsubstituted, mono- or di-substituted heteroaromatic group        chosen from pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl,        thienyl, benzothien-2-yl, benzothien-3-yl, dibenzofuranyl,        dibenzothienyl, carbazoyl, benzopyridyl, indolinyl and        fluorenyl; wherein the aryl and heteroaromatic substituents are        each independently:        -   hydroxy, aryl, mono- or di-(C₁-C₁₂)alkoxyaryl, mono- or            di-(C₁-C₁₂)alkylaryl, haloaryl, C₃-C₇ cycloalkylaryl, C₃-C₇            cycloalkyl, C₃-C₇ cycloalkyloxy, C₃-C₇            cycloalkyloxy(C₁-C₁₂)alkyl, C₃-C₇            cycloalkyloxy(C₁-C₁₂)alkoxy, aryl(C₁-C₁₂)alkyl,            aryl(C₁-C₁₂)alkoxy, aryloxy, aryloxy(C₁-C₁₂)alkyl,            aryloxy(C₁-C₁₂)alkoxy, mono- or            di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono- or            di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, mono- or            di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, mono- or            di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy, amino, mono- or            di-(C₁-C₁₂)alkylamino, diarylamino, piperazino,            N—(C₁-C₁₂)alkylpiperazino, N-arylpiperazino, aziridino,            indolino, piperidino, morpholino, thiomorpholino,            tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,            C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy,            mono(C₁-C₁₂)alkoxy(C₁-C₁₂)alkyl, acryloxy, methacryloxy,            halogen, or —C(═O)R²¹ wherein R²¹ is —OR²², —N(R²³)R²⁴,            piperidino or morpholino, wherein R²² is allyl, C₁-C₆ alkyl,            phenyl, mono(C₁-C₆)alkyl substituted phenyl,            mono(C₁-C₆)alkoxy substituted phenyl, phenyl(C₁-C₃)alkyl,            mono(C₁-C₆)alkyl substituted phenyl(C₁-C₃)alkyl,            mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl, C₁-C₆            alkoxy(C₂-C₄)alkyl or C₁-C₆ haloalkyl, and R²³ and R²⁴ are            each independently C₁-C₆ alkyl, C₅-C₇ cycloalkyl or a            substituted or unsubstituted phenyl, said phenyl            substituents independently being C₁-C₆ alkyl or C₁-C₆            alkoxy;    -   an unsubstituted or mono-substituted group chosen from        pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidyl,        phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, said        substituents being C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, phenyl or        halogen; a mono-substituted phenyl, said phenyl having a        substituent located at the para position, the substituent being        a dicarboxylic acid residue or derivative thereof, a diamine        residue or derivative thereof, an amino alcohol residue or        derivative thereof, a polyol residue or derivative thereof,        —(CH₂)—, —(CH₂)_(t) or —[O—(CH₂)_(t)]_(k)—, wherein t ranges        form 2 to 6 and k ranges from 1 to 50, and wherein the        substituent is connected to an aryl group on another        photochromic material;    -   a group represented by:

-   -   wherein V is —CH₂— or —O—, W is oxygen or substituted nitrogen,        provided that when W is substituted nitrogen, V is —CH₂—, the        substituted nitrogen substituents being hydrogen, C₁-C₁₂ alkyl        or C₁-C₁₂ acyl, each R²⁵ independently being C₁-C₁₂ alkyl,        C₁-C₁₂ alkoxy, hydroxy or halogen, R²⁶ and R²⁷ are each        independently hydrogen or C₁-C₁₂ alkyl, and s ranges from 0 to        2; or a group represented by:

-   -   wherein R²⁸ is hydrogen or C₁-C₁₂ alkyl, and R²⁹ is an        unsubstituted, mono- or di-substituted naphthyl, phenyl, furanyl        or thienyl, said substituents being C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy        or halogen; or    -   B and B′ taken together form a fluoren-9-ylidene or mono- or        di-substituted fluoren-9-ylidene, each of said fluoren-9-ylidene        substituents independently being C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or        halogen.

Further, the photochromic material described herein can comprise atleast one of a reactive substituent and a compatiblizing substituent,each of the reactive substituent or compatiblizing substituent beingindependently represented by one of:

-A′-D-E-G-J; -G-E-G-J; -D-E-G-J; -A′-D-J; -D-G-J; -D-J; -A′-G-J; -G-J;and -A′-J;wherein:

-   -   (i) each -A′- is independently —O—, —C(═O)—, —CH₂—, —OC(═O)— or        —NHC(═O)—, provided that if -A′- is —O—, -A′- forms at least one        bond with -J;    -   (ii) each -D- is independently:        -   (a) a diamine residue or a derivative thereof, the diamine            residue being an aliphatic diamine residue, a cyclo            aliphatic diamine residue, a diazacycloalkane residue, an            azacyclo aliphatic amine residue, a diazacrown ether residue            or an aromatic diamine residue, wherein a first amino            nitrogen of the diamine residue forms a bond with -A′-, the            group that extends the pi-conjugated system of the            indeno-fused naphthopyran bonded at the 11-position thereof,            or a substituent or an available position on the            indeno-fused naphthopyran, and a second amino nitrogen of            the diamine residue forms a bond with -E-, -G- or -J; or        -   (b) an amino alcohol residue or a derivative thereof, the            amino alcohol residue being an aliphatic amino alcohol            residue, a cyclo aliphatic amino alcohol residue, an            azacyclo aliphatic alcohol residue, a diazacyclo aliphatic            alcohol residue or an aromatic amino alcohol residue,            wherein an amino nitrogen of the amino alcohol residue forms            a bond with -A′-, the group that extends the pi-conjugated            system of the indeno-fused naphthopyran bonded at the            11-position thereof, or a substituent or an available            position on the indeno-fused naphthopyran, and an alcohol            oxygen of said amino alcohol residue forms a bond with -E-,            -G- or -J, or the amino nitrogen of the amino alcohol            residue forms a bond with -E-, -G- or -J, and the alcohol            oxygen of the amino alcohol residue forms a bond with -A′-,            the group that extends the pi-conjugated system of the            indeno-fused naphthopyran bonded at the 11-position thereof,            or a substituent or an available position on the            indeno-fused naphthopyran;    -   (iii) each -E- is independently a dicarboxylic acid residue or a        derivative thereof, said dicarboxylic acid residue being an        aliphatic dicarboxylic acid residue, a cycloaliphatic        dicarboxylic acid residue or an aromatic dicarboxylic acid        residue, wherein a first carbonyl group of the dicarboxylic acid        residue forms a bond with -G- or -D-, and a second carbonyl        group of the dicarboxylic acid residue forms a bond with -G-;    -   (iv) each -G- is independently:        -   (a) —[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]—O—, wherein x, y            and z are each independently chosen and range from 0 to 50,            and a sum of x, y, and z ranges from 1 to 50;        -   (b) a polyol residue or a derivative thereof, the polyol            residue being an aliphatic polyol residue, a cyclo aliphatic            polyol residue or an aromatic polyol residue, wherein a            first polyol oxygen of said polyol residue forms a bond with            -A′-, -D-, -E-, the group that extends the pi-conjugated            system of the indeno-fused naphthopyran bonded at the            11-position thereof, or a substituent or an available            position on the indeno-fused naphthopyran, and a second            polyol oxygen of said polyol forms a bond with -E- or -J; or        -   (c) a combination thereof, wherein the first polyol oxygen            of the polyol residue forms a bond with a group            —[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]— and the second polyol            oxygen forms a bond with -E- or -J; and    -   (v) each -J is independently:        -   (a) a group —K, wherein —K is —CH₂COOH, —CH(CH₃)COOH,            —C(O)(CH₂)_(w)COOH, —C₆H₄SO₃H, —C₅H₁₀SO₃H, —C₄H₈SO₃H,            —C₃H₆SO₃H, —C₂H₄SO₃H or —SO₃H, wherein w ranges from 1 to            18;        -   (b) hydrogen, provided that if is hydrogen, -J is bonded to            an oxygen of -D- or -G-, or a nitrogen of -D-; or        -   (c) a group -L or residue thereof, wherein -L is acryl,            methacryl, crotyl, 2-(methacryloxy)ethylcarbamyl,            2-(methacryloxy)ethoxycarbonyl, 4-vinylphenyl, vinyl,            1-chlorovinyl or epoxy.

At least one of an R^(e) group at the 6-position, an R^(e) group at the7-position, B, B′, R^(b), R^(c) and R^(a) comprises a reactivesubstituent.

In a particular embodiment of the present invention, the photochromicmaterial can be represented by graphic formula I wherein:

-   -   (i) each of an R^(e) group at the 7-position and an R^(e) group        at the 6-position is independently —OR¹⁰ wherein R¹⁰ is C₁-C₆        alkyl, a substituted or unsubstituted phenyl, said phenyl        substituents being C₁-C₆ alkyl or C₁-C₆ alkoxy,        phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl substituted        phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substituted        phenyl(C₁-C₃)alkyl, (C₁-C₆)alkoxy(C₂-C₄)alkyl, C₃-C₇ cycloalkyl        or mono(C₁-C₄)alkyl substituted C₃-C₇ cycloalkyl; —N(R¹¹)R¹²        wherein R¹¹ and R¹² are each independently hydrogen, C₁-C₅        alkyl, C₁-C₈ alkylaryl, C₃-C₂₀ cycloalkyl, C₄-C₂₀ bicycloalkyl,        C₅-C₂₀ tricycloalkyl or C₁-C₂₀ alkoxyalkyl, wherein said aryl        group is phenyl or naphthyl; a nitrogen containing ring        represented by:

-   -    wherein each -M- is independently chosen for each occurrence        from —CH₂—, —CH(R¹³)—, —C(R¹³)₂—, —CH(aryl)-, —C(aryl)₂- and        —C(R¹³)(aryl)-, and -Q- is -M-, —O—, —S—, —NH—, —N(R¹³)— or        —N(aryl)-, wherein each R¹³ is independently C₁-C₆ alkyl, each        (aryl) is independently phenyl or naphthyl, u ranges from 1 to        3, and v ranges from 0 to 3, provided that if v is 0, -Q- is        -M-; or a reactive substituent or a compatiblizing substituent,        provided that the reactive or compatiblizing substituent        comprises a linking group comprising an aliphatic amino alcohol        residue, a cyclo aliphatic amino alcohol residue, an azacyclo        aliphatic alcohol residue, a diazacyclo aliphatic alcohol        residue, a diamine residue, an aliphatic diamine residue, a        cyclo aliphatic diamine residue, a diazacycloalkane residue, an        azacyclo aliphatic amine residue, an oxyalkoxy group, an        aliphatic polyol residue or a cyclo aliphatic polyol residue        that forms a bond with the indeno[2′,3′:3,4]naphtho[1,2-b]pyran        at the 6-position or the 7-position; or    -   (ii) an R^(e) group in the 6-position and an R^(e) group in the        7-position of the indeno[2′,3′:3,4]naphtho[1,2-b]pyran together        form a group represented by:

wherein Z and Z′ are each independently oxygen or —NR¹¹—, wherein R¹¹ isas set forth above in (i).

For example, the photochromic material can be chosen from:

-   -   (i)        3,3-di(4-methoxyphenyl)-6,7-dimethoxy-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (ii)        3,3-di(4-methoxyphenyl)-6,7-dimethoxy-11-(3,5-bis(trifluoromethyl)phenyl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (iii)        3,3-di(4-methoxyphenyl)-6,7-dimethoxy-11-(2-trifluoromethyl)phenyl-13,13-diethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (iv)        3,3-di-(4-methoxyphenyl)-6-methoxy-7-piperidino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (v)        3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7-dimethoxy-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (vi)        3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6-methoxy-7-piperidino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (vii)        3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6-methoxy-7-morpholino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (viii)        3,3-di(4-hydroxyphenyl)-6,7-dimethoxy-11-(3,5-bis(trifluoromethyl)phenyl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (ix)        3,3-di-(4-methoxyphenyl-6-methoxy-7-morpholino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (x)        3,3-bis(4-methoxyphenyl)-6,7-dimethoxy-11-(2-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (xi)        3,3-bis(4-methoxyphenyl)-6-methoxy-7-piperidino-11-(2-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (xii)        3-phenyl-3′-(4-morpholinophenyl)-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (xiii)        3-(4-morpholinophenyl)-3-phenyl-11-(2-trifluoromethyl)-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran;    -   (xiv)        3-(4-butoxyphenyl)-3-(4-methoxyphenyl)-6,7-dimethoxy-11-(3-(trifluoromethyl)pyridin-2-yl)-13,13-dimethyl-3H,13H-indeno[2′,3′3,4]naphtho[1,2-b]pyran    -   (xv) and mixtures thereof.

Also, where the photochromic material comprising the group that extendsthe pi-conjugated system bonded at the 11-position thereof comprises anadditional photochromic material that is linked thereto, the additionalphotochromic material may be linked to the photochromic materialcomprising the group that extends the pi-conjugated system bonded at the11-position thereof by an insulating group. As used herein, the term“insulating group” means a group having at least two consecutive sigma(6) bonds that separate the pi-conjugated systems of the photochromicmaterials. For example, the insulating group may be the alkyl portion ofa piperazino group or the alkyl portion of an oxyalkoxy group.

Still further, and as discussed in more detail below, according tovarious non-limiting embodiments, the group that extends thepi-conjugated system of the indeno-fused naphthopyran bonded at the11-position also may comprise a reactive substituent or a compatiblizingsubstituent. As used herein the term “reactive substituent” means anarrangement of atoms, wherein a portion of the arrangement comprises areactive moiety or a residue thereof. As used herein, the term “moiety”means a part or portion of an organic molecule that has a characteristicchemical property. As used herein, the term “reactive moiety” means apart or portion of an organic molecule that may react to form one ormore bond(s) with an intermediate in a polymerization reaction, or witha polymer into which it has been incorporated. As used herein the term“intermediate in a polymerization reaction” means any combination of twoor more monomer units that are capable of reacting to form one or morebond(s) to additional monomer unit(s) to continue a polymerizationreaction or, alternatively, reacting with a reactive moiety of thereactive substituent on the photochromic material. For example, althoughnot limiting herein, the reactive moiety may react with an intermediatein a polymerization reaction of a monomer or oligomer as a co-monomer inthe polymerization reaction or may react as, for example and withoutlimitation, a nucleophile or electrophile, that adds into theintermediate. Alternatively, the reactive moiety may react with a group(such as, but not limited to a hydroxyl group) on a polymer.

As used herein the term “residue of a reactive moiety” means that whichremains after a reactive moiety has been reacted with a protecting groupor an intermediate in a polymerization reaction. As used herein the term“protecting group” means a group that is removably bonded to a reactivemoiety that prevents the reactive moiety from participating in areaction until the group is removed. Optionally, the reactivesubstituents according to various non-limiting embodiments disclosedherein may further comprise a linking group. As used herein the term“linking group” means one or more group(s) or chain(s) of atoms thatconnect the reactive moiety to the photochromic material.

As used herein the term “compatiblizing substituent” means anarrangement of atoms that can facilitate integration of the photochromicmaterial into another material or solvent. For example, according tovarious non-limiting embodiments disclosed herein, the compatiblizingsubstituent may facilitate integration of the photochromic material intoa hydrophilic material by increasing the miscibility of the photochromicmaterial in water or a hydrophilic polymeric, oligomeric, or monomericmaterial. According to other non-limiting embodiments, thecompatiblizing substituent may facilitate integration of thephotochromic material into a lipophilic material. Although not limitingherein, photochromic materials according to various non-limitingembodiments disclosed herein that comprise a compatiblizing substituentthat facilitates integration into a hydrophilic material may be misciblein hydrophilic material at least to the extent of one gram per liter.Non-limiting examples of compatiblizing substitutents include thosesubstitutents comprising the group -J, where -J represents the group —Kor hydrogen, which are discussed herein below.

Further, it should be appreciated that some substituents may be bothcompatiblizing and reactive. For example, a substituent that compriseshydrophilic linking group(s) that connects a reactive moiety to thephotochromic material may be both a reactive substituent and acompatiblizing substituent. As used herein, such substituents may betermed as either a reactive substituent or a compatiblizing substituent.

Further, according to any of the previously mentioned non-limitingembodiments, the indeno-fused naphthopyran may be free of spiro-cyclicgroups at the 13-position of the indeno-fused naphthopyran. As usedherein the phrase “free of spiro-cyclic groups at the 13-position” meansthat if the 13-position of the indeno-fused naphthopyran isdi-substituted, the substituent groups do not together form aspiro-cyclic group.

Further, various non-limiting embodiments disclosed herein relate tophotochromic materials comprising an indeno-fused naphthopyran and agroup that extends the pi-conjugated system of the indeno-fusednaphthopyran bonded at the 11-position thereof (as discussed above),wherein the indeno-fused naphthopyran is anindeno[2′,3′:3,4]naphtho[1,2-b]pyran, and wherein the 6-position and/orthe 7-position of the indeno-fused naphthopyran may each independentlybe substituted with a nitrogen containing group or an oxygen containinggroup (R^(e)); and the 13-position of the indeno-fused naphthopyran maybe di-substituted with R^(s) and R^(c). Other non-limiting embodimentsdisclosed herein relate to photochromic materials comprising anindeno-fused naphthopyran, wherein the 13-position of the indeno-fusednaphthopyran is unsubstituted, mono-substituted or di-substituted,provided that if the 13-position of the indeno-fused naphthopyran isdi-substituted, the substituent groups do not together form norbornyl,and wherein the photochromic material has an integrated extinctioncoefficient greater than 1.0×10⁶ nm×mol⁻¹×cm⁻¹ as determined byintegration of a plot of extinction coefficient of the photochromicmaterial vs. wavelength over a range of wavelengths ranging from 320 nmto 420 nm, inclusive. Further, according to these non-limitingembodiments the integrated extinction coefficient may range from 1.1×10⁶to 4.0×10⁶ nm×mol⁻¹×cm⁻¹ as determined by integration of a plot ofextinction coefficient of the photochromic material vs. wavelength overa range of wavelengths ranging from 320 nm to 420 nm, inclusive. Stillfurther, the photochromic materials according these non-limitingembodiments may comprise a group that extends the pi-conjugated systemof the indeno-fused naphthopyran bonded at the 11-position thereof.Non-limiting examples of groups bonded at the 11-position of theindeno-fused naphthopyran that extend the pi-conjugated system of theindeno-fused naphthopyran include those discussed above.

One specific non-limiting embodiment disclosed herein provides aphotochromic material comprising: (i) an indeno-fused naphthopyranchosen from an indeno[2′,3′:3,4]naphtho[1,2-b]pyran, anindeno[1′,2′:4,3]naphtho[2,1-b]pyran, and mixtures thereof, wherein the13-position of the indeno-fused naphthopyran is unsubstituted,mono-substituted or di-substituted, provided that if the 13-position ofthe indeno-fused naphthopyran is di-substituted, the substituent groupsdo not together form norbornyl; and (ii) a group having at least onependant halo-substituted group bonded thereto that extends thepi-conjugated system of the indeno-fused naphthopyran bonded at the11-position thereof.

As previously discussed, any of the photochromic materials according tovarious non-limiting embodiments disclosed herein may comprise at leastone of a reactive substituent and/or a compatiblizing substituent.Further, according to various non-limiting embodiments disclosed hereinwherein the photochromic material comprises multiple reactivesubstituents and/or multiple compatiblizing substituents, each reactivesubstituent and each compatiblizing substituent may be independentlychosen. Non-limiting examples of reactive and/or compatiblizingsubstituents that may be used in conjunction with the variousnon-limiting embodiments disclosed herein include those discussed above.

Non-limiting examples of groups that -A′- may represent according tovarious non-limiting embodiments disclosed herein include —O—, —C(═O)—,—CH₂—, —OC(═O)— and —NHC(═O)—, provided that if -A′- represents —O—,-A′- forms at least one bond with -J.

Non-limiting examples of groups that —O— may represent according tovarious non-limiting embodiments include a diamine residue or aderivative thereof, wherein a first amino nitrogen of said diamineresidue may form a bond with -A′-, the group that extends thepi-conjugated system of the indeno-fused naphthopyran bonded at the11-position thereof, or a substituent or an available position on theindeno-fused naphthopyran, and a second amino nitrogen of said diamineresidue may form a bond with -E-, -G- or -J; and an amino alcoholresidue or a derivative thereof, wherein an amino nitrogen of said aminoalcohol residue may form a bond with -A′-, the group that extends thepi-conjugated system of the indeno-fused naphthopyran bonded at the11-position thereof, or a substituent or an available position on theindeno-fused naphthopyran, and an alcohol oxygen of said amino alcoholresidue may form a bond with -E-, -G- or -J. Alternatively, according tovarious non-limiting embodiments disclosed herein the amino nitrogen ofsaid amino alcohol residue may form a bond with -E-, -G- or -J, and saidalcohol oxygen of said amino alcohol residue may form a bond with -A′-,the group that extends the pi-conjugated system of the indeno-fusednaphthopyran bonded at the 11-position thereof, or a substituent or anavailable position on the indeno-fused naphthopyran.

Non-limiting examples of suitable diamine residues that -D- mayrepresent include an aliphatic diamine residue, a cyclo aliphaticdiamine residue, a diazacycloalkane residue, an azacyclo aliphatic amineresidue, a diazacrown ether residue, and an aromatic diamine residue.Specific non-limiting examples diamine residues that may be used inconjunction with various non-limiting embodiments disclosed hereininclude the following:

Non-limiting examples of suitable amino alcohol residues that -D- mayrepresent include an aliphatic amino alcohol residue, a cyclo aliphaticamino alcohol residue, an azacyclo aliphatic alcohol residue, adiazacyclo aliphatic alcohol residue and an aromatic amino alcoholresidue. Specific non-limiting examples amino alcohol residues that maybe used in conjunction with various non-limiting embodiments disclosedherein include the following:

According to various non-limiting embodiments disclosed herein, -E- mayrepresent a dicarboxylic acid residue or a derivative thereof, wherein afirst carbonyl group of said dicarboxylic acid residue may form a bondwith -G- or —O—, and a second carbonyl group of said dicarboxylic acidresidue may form a bond with -G-. Non-limiting examples of suitabledicarboxylic acid residues that -E- may represent include an aliphaticdicarboxylic acid residue, a cycloaliphatic dicarboxylic acid residueand an aromatic dicarboxylic acid residue. Specific non-limitingexamples of dicarboxylic acid residues that may be used in conjunctionwith various non-limiting embodiments disclosed herein include thefollowing:

According to various non-limiting embodiments disclosed herein, -G- mayrepresent a group —[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]—O—, wherein x, yand z are each independently chosen and range from 0 to 50, and a sum ofx, y, and z ranges from 1 to 50; a polyol residue or a derivativethereof, wherein a first polyol oxygen of said polyol residue may form abond with -A′-, -D-, -E-, the group that extends the pi-conjugatedsystem of the indeno-fused naphthopyran bonded at the 11-positionthereof, or a substituent or an available position on the indeno-fusednaphthopyran, and a second polyol oxygen of said polyol may form a bondwith -E- or -J; or a combination thereof, wherein the first polyoloxygen of the polyol residue forms a bond with a group—[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]— (i.e., to form the group—[(OC₂H₄)_(x)(OC₃H₆)_(y)(OC₄H₈)_(z)]—O—), and the second polyol oxygenforms a bond with -E- or -J. Non-limiting examples of suitable polyolresidues that -G- may represent include an aliphatic polyol residue, acyclo aliphatic polyol residue and an aromatic polyol residue.

Specific non-limiting examples of polyols from which the polyol residuesthat -G- may represent may be formed according to various non-limitingembodiments disclosed herein include (a) low molecular weight polyolshaving an average molecular weight less than 500, such as, but notlimited to, those set forth in U.S. Pat. No. 6,555,028 at col. 4, lines48-50, and col. 4, line 55 to col. 6, line 5, which disclosure is herebyspecifically incorporated by reference herein; (b) polyester polyols,such as, but not limited to, those set forth in U.S. Pat. No. 6,555,028at col. 5, lines 7-33, which disclosure is hereby specificallyincorporated by reference herein; (c) polyether polyols, such as but notlimited to those set forth in U.S. Pat. No. 6,555,028 at col. 5, lines34-50, which disclosure is hereby specifically incorporated by referenceherein; (d) amide-containing polyols, such as, but not limited to, thoseset forth in U.S. Pat. No. 6,555,028 at col. 5, lines 51-62, whichdisclosure is hereby specifically incorporated by reference; (e) epoxypolyols, such as, but not limited to, those set forth in U.S. Pat. No.6,555,028 at col. 5 line 63 to col. 6, line 3, which disclosure ishereby specifically incorporated by reference herein; (f) polyhydricpolyvinyl alcohols, such as, but not limited to, those set forth in U.S.Pat. No. 6,555,028 at col. 6, lines 4-12, which disclosure is herebyspecifically incorporated by reference herein; (g) urethane polyols,such as, but not limited to those set forth in U.S. Pat. No. 6,555,028at col. 6, lines 13-43, which disclosure is hereby specificallyincorporated by reference herein; (h) polyacrylic polyols, such as, butnot limited to those set forth in U.S. Pat. No. 6,555,028 at col. 6,lines 43 to col. 7, line 40, which disclosure is hereby specificallyincorporated by reference herein; (i) polycarbonate polyols, such as,but not limited to, those set forth in U.S. Pat. No. 6,555,028 at col.7, lines 41-55, which disclosure is hereby specifically incorporated byreference herein; and (j) mixtures of such polyols.

According to various non-limiting embodiments disclosed herein, -J mayrepresent a group —K, wherein —K represents a group such as, but notlimited to, —CH₂COOH, —CH(CH₃)COOH, —C(O)(CH₂)_(w)COOH, —C₆H₄SO₃H,—C₆H₁₀SO₃H, —C₄H₈SO₃H, —C₃H₆SO₃H, —C₂H₄SO₃H and —SO₃H, wherein “w”ranges from 1 to 18. According to other non-limiting embodiments -J mayrepresent hydrogen that forms a bond with an oxygen or a nitrogen oflinking group to form a reactive moiety such as —OH or —NH. For example,according to various non-limiting embodiments disclosed herein, -J mayrepresent hydrogen, provided that if -J represents hydrogen, -J isbonded to an oxygen of -D- or -G-, or a nitrogen of -D-.

According to still other non-limiting embodiments, -J may represent agroup -L or residue thereof, wherein -L may represent a reactive moiety.For example, according to various non-limiting embodiments disclosedherein -L may represent a group such as, but not limited to, acryl,methacryl, crotyl, 2-(methacryloxy)ethylcarbamyl,2-(methacryloxy)ethoxycarbonyl, 4-vinylphenyl, vinyl, 1-chlorovinyl orepoxy. As used herein, the terms acryl, methacryl, crotyl,2-(methacryloxy)ethylcarbamyl, 2-(methacryloxy)ethoxycarbonyl,4-vinylphenyl, vinyl, 1-chlorovinyl, and epoxy refer to the followingstructures:

As previously discussed, -G- may represent a residue of a polyol, whichis defined herein to include hydroxy-containing carbohydrates, such asthose set forth in U.S. Pat. No. 6,555,028 at col. 7, line 56 to col. 8,line 17, which disclosure is hereby specifically incorporated byreference herein. The polyol residue may be formed, for example andwithout limitation herein, by the reaction of one or more of the polyolhydroxyl groups with a precursor of -A′-, such as a carboxylic acid or amethylene halide, a precursor of polyalkoxylated group, such aspolyalkylene glycol, or a hydroxyl substituent of the indeno-fusednaphthopyran. The polyol may be represented by q-(OH)_(a) and theresidue of the polyol may be represented by the formula —O-q-(OH)_(a-1),wherein q is the backbone or main chain of the polyhydroxy compound and“a” is at least 2.

Further, as discussed above, one or more of the polyol oxygens of -G-may form a bond with -J (i.e., forming the group -G-J). For example,although not limiting herein, wherein the reactive and/or compatiblizingsubstituent comprises the group -G-J, if -G- represents a polyol residueand -J represents a group —K that contains a carboxyl terminating group,-G-J may be produced by reacting one or more polyol hydroxyl groups toform the group —K (for example as discussed with respect to Reactions Band C at col. 13, line 22 to col. 16, line 15 of U.S. Pat. No.6,555,028, which disclosure is hereby specifically incorporated byreference herein) to produce a carboxylated polyol residue.Alternatively, if -J represents a group —K that contains a sulfo orsulfono terminating group, although not limiting herein, -G-J may beproduced by acidic condensation of one or more of the polyol hydroxylgroups with HOC₆H₄SO₃H; HOC₆H₁₀SO₃H; HOC₄H₈SO₃H; HOC₃H₆SO₃H; HOC₂H₄SO₃H;or H₂SO₄, respectively. Further, although not limiting herein, if -G-represents a polyol residue and -J represents a group -L chosen fromacryl, methacryl, 2-(methacryloxy)ethylcarbamyl and epoxy, -L may beadded by condensation of the polyol residue with acryloyl chloride,methacryloyl chloride, 2-isocyanatoethyl methacrylate orepichlorohydrin, respectively.

As discussed above, according to various non-limiting embodimentsdisclosed herein, a reactive substituent and/or a compatiblizingsubstituent may be bonded to group that extends the pi-conjugated systemof the indeno-fused naphthopyran bonded at the 11-position of theindeno-fused naphthopyran. For example, as discussed above, the groupthat extends the pi-conjugated system of the indeno-fused naphthopyranbonded at the 11-position thereof may be an aryl or heteroaryl that issubstituted with the reactive and/or compatiblizing substituent.

For example, the group that extends the pi-conjugated system may be asubstituted aryl group (e.g., a phenyl group substituted with atrifluoromethyl) that is further substituted with a reactive substituent(e.g., a (2-methacryloxyethoxy)carbonyl which may be represented by-A′-G-J (as discussed above), wherein -A′- represents —C(═O)—, -G-represents —[OC₂H₄]O—, and -J represents methacryl.

Additionally or alternatively, a reactive and/or compatiblizingsubstituent may be bonded at a substituent or an available position onthe indeno-fused naphthopyran ring other than at the 11-position. Forexample, although not limiting herein, in addition to or instead ofhaving a reactive and/or compatiblizing substituent bonded to the groupthat extends the pi-conjugated system of the indeno-fused naphthopyranbonded at the 11-position of the indeno-fused naphthopyran, the13-position of the indeno-fused naphthopyran may be mono- ordi-substituted with a reactive and/or compatiblizing substituent.Further, if the 13-position is di-substituted, each substituent may bethe same or different. In another non-limiting example, in addition toor instead of having a reactive and/or compatiblizing substituent bondedto the group that extends the pi-conjugated system of the indeno-fusednaphthopyran bonded at the 11-position of the indeno-fused naphthopyran,a reactive and/or compatiblizing substituent may be substituted at the3-position of an indeno[2′,3′:3,4]naphtho[1,2-b]pyran, the 2-position ofan indeno[1′,2′:4,3]naphtho[2,1-b]pyran, and/or the 6- or 7-positions ofthese indeno-fused naphthopyrans. Further, if the photochromic materialcomprises more than one reactive and/or compatiblizing substituent, eachreactive and/or compatiblizing substituent may be the same as ordifferent from one or more of the remaining reactive and/orcompatiblizing substituents.

For example, according to one non-limiting embodiment, the group thatextends the pi-conjugated system of the indeno-fused naphthopyran bondedat the 11-position thereof can be a substituted aryl group and thephotochromic material further comprises a reactive substituent (e.g., a3-(2-methacryloxyethyl)carbamyloxymethylenepiperidino-1-yl) group whichmay be represented by -D-J (as discussed above), wherein -D- representsan azacyclo aliphatic alcohol residue, wherein the nitrogen of theazacyclo aliphatic alcohol residue forms a bond with the indeno-fusednaphthopyran at the 7-position, and the alcohol oxygen of the azacycloaliphatic alcohol residue forms a bond with -J, wherein -J represents2-(methacryloxy)ethylcarbamyl. Another non-limiting example of aphotochromic material according to various non-limiting embodimentsdisclosed herein that has a reactive substituent at the 7-positionthereof is a3-(4-morpholinophenyl)-3-phenyl-6-methoxy-7-(3-(2-methacryloxyethyl)carbamyloxymethylenepiperidino-1-yl)-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

One non-limiting example of a photochromic material according to variousnon-limiting embodiments disclosed herein that has a reactivesubstituent at the 3-position thereof is a3-(4-(2-(2-methacryloxyethyl)carbamylethoxy)phenyl)-3-phenyl-6,7-dimethoxy-11-(2-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Additional description of reactive substituents that may be used inconnection with the photochromic materials described herein is set forthat col. 5, line 42 to col. 15, line 28, in U.S. Pat. No. 7,556,750,entitled PHOTOCHROMIC MATERIALS WITH REACTIVE SUBSTITUENTS, which ishereby specifically incorporated by reference herein. Still othernon-limiting examples of reactive and/or compatiblizing substituents areset forth in U.S. Pat. No. 6,555,028, at col. 3, line 45 to col. 4, line26, and U.S. Pat. No. 6,113,814 at col. 3, lines 30-64, whichdisclosures are hereby specifically incorporated by reference herein.

Methods of making photochromic materials that include the indeno-fusednaphthopyrans according to the present invention are described here withreference to the general reaction schemes summarized and depicted inFIGS. 1 through 5 of the drawings. With reference to FIG. 1, there isdepicted a reaction scheme for making substituted7H-benzo[C]fluoren-5-ol compounds, that may be further reacted as shownin FIGS. 2 through 5 to form photochromic materials comprising anindeno-fused naphthopyran and a pendent halo-substituted groupsubstituted pi-conjugation extending group bonded to the 11-positionthereof, that extends the pi-conjugated system of the indeno-fusednaphthopyran. The reaction schemes depicted in FIGS. 1-5 are presentedfor purposes of illustration, and as such are not intended to belimiting with regard to the scope of the present invention.

With reference to FIG. 1, a solution of a γ-substituted benzoylchloride, represented by structure (a) in FIG. 1, and benzene,represented by structure (b) in FIG. 1, which may have one or moresubstituents γ¹, in methylene chloride are added to a reaction flask.Suitable γ¹-substituents include, for example and without limitation,halogen. Suitable γ¹ substituents include, for example and withoutlimitation, those groups as described previously herein with regard toR^(e), depending on what position a particular γ¹ substituent is bondedto. Anhydrous aluminum chloride catalyzes the Friedel-Crafts acylationto give a substituted benzophenone represented by structure (c) inFIG. 1. This material is then reacted in a Stobbe reaction with dimethylsuccinate to produce a mixture of half-esters, one of which isrepresented by structure (d) in FIG. 1. Thereafter the half-esters arereacted in acetic anhydride and toluene at an elevated temperature toproduce, after recrystallization, a mixture of substituted naphthalenecompounds, one of which is represented by structure (e) in FIG. 1. Themixture of substituted naphthalene compounds is then reacted with methylmagnesium chloride to produce a mixture of substituted naphthalenecompounds, one of which is represented by structure (f) in FIG. 1. Themixture of substituted naphthalene compounds is then cyclized withdodecylbenzene sulfonic acid to afford a mixture of7H-benzo[C]fluoren-5-ol compounds, one of which is represented bystructure (g) in FIG. 1.

With reference to FIG. 2, the 7H-benzo[C]fluoren-5-ol compoundrepresented by structure (g) may be reacted with a phenyl boronic acidrepresented by structure (O), which may be substituted with a pendenthalo-substituted group represented by γ³ as shown in FIG. 2, to form the9-(4-γ³-phenyl)-7H-benzo[C]fluoren-5-ol compound represented bystructure (p) in FIG. 2. Examples of suitable boronic acids include,without limitation, 4-(trifluoromethyl)phenylboronic acid, and4-(perfluoroethyl)phenylboronic acid. The compound represented bystructure (p) may be further reacted with a propargyl alcoholrepresented by structure (i) to produce the indeno-fused naphthopyran(represented by structure (q) in FIG. 2), wherein a pendenthalo-substituted group substituted phenyl group that extends thepi-conjugated system of the indeno-fused naphthopyran is bonded at the11-position thereof. Although not required, according to variousnon-limiting embodiments disclosed herein and as shown in FIG. 2, thephenyl group bonded at the 11-position may be further substituted, inaddition to the one or more pendent halo-substituted groups (asdescribed previously herein, for example, with regard to R^(a)).Further, the substituted phenyl at the 11-position may, in addition tothe pendent halo-substituted group, have up to four substituents, andthose substituents may be a variety of different substituents at any ofthe positions ortho, meta or para to the indeno-fused naphthopyran.

With reference to FIG. 3, the 7H-benzo[C]fluoren-5-ol compoundrepresented by structure (g) may be coupled in the presence of apalladium catalysis with a terminal alkyne group represented bystructure (r), which may be substituted with a pendent halo-substitutedgroup represented by γ⁴ as shown in FIG. 3, to form the9-alkynyl-7H-benzo[C]fluoren-5-ol compound represented by structure‘(s)’ in FIG. 3. Suitable terminal alkynes include, for example,trifluoromethyl-acetylene and perfluoroethyl-acetylene. The compoundrepresented by structure ‘(s)’ may be further reacted with a propargylalcohol represented by structure (i) to produce the indeno-fusednaphthopyran (represented by structure (t) in FIG. 3) having a pendenthalo-substituted group substituted alkynyl group that extends thepi-conjugated system of the indeno-fused naphthopyran bonded at the11-position thereof.

With reference to FIG. 4, the 7H-benzo[C]fluoren-5-ol compoundrepresented by structure (g) may be reacted with an alkene representedby structure (u), which may be substituted with a pendenthalo-substituted group represented by γ⁵ as shown in FIG. 4, to form the9-alkenyl-7H-benzo[C]fluoren-5-ol compound represented by structure (v)in FIG. 4. Examples of suitable alkenes include, without limitationtrifluoromethyl-ethene and perfluoroethyl-ethene. The compoundrepresented by structure (v) may be further reacted with a propargylalcohol represented by structure (i) to produce the indeno-fusednaphthopyran (represented by structure (w) in FIG. 4) having a pendenthalo-substituted group substituted alkenyl group that extends thepi-conjugated system of the indeno-fused naphthopyran bonded at the11-position thereof.

With reference to FIG. 5, the 7H-benzo[C]fluoren-5-ol compoundrepresented by structure (g) is reacted with4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) representedby structure (o′) in the presence of a palladium catalyst to form thecompound represented by structure (t′). The latter can be reacted with ahalogenated heteroaryl represented by structure (u′) in which isnitrogen or carbon provided that at least one D is nitrogen and the halogroup is chosen from Br, Cl or I, and which is substituted with apendent halo-substituted group represented by γ³ to form the compoundrepresented by structure (v′). An example of a suitable halogenatedheteroaryl group represented by structure (u′) is3-(trifluoromethyl)-2-bromopyridine. The compound represented bystructure (v′) may be further reacted with a propargyl alcoholrepresented by structure (i) to produce the indeno-fused naphthopyranrepresented by structure (w′).

With reference to FIGS. 6-8, each graphic formula represents a compoundof the present invention. FIG. 6 represents3,3-di-(4-methoxyphenyl-6-methoxy-7-piperidino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyranincluded herein as Example 4. FIG. 7 represents3,3-di(4-methoxyphenyl)-6,7-dimethoxy-11-(3,5-bis(trifluoromethyl)phenyl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyranincluded herein as Example 2. FIG. 8 represents3-(4-butoxyphenyl)-3-(4-methoxyphenyl)-6,7-dimethoxy-11-(3-(trifluoromethyl)pyridin-2-yl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyranincluded herein as Example 13.

Further, non-limiting examples of methods of forming benzofurano-fusednaphthopyrans, indolo-fused naphthopyrans, and/or benzothieno-fusednaphthopyrans that may be useful (with appropriate modifications thatwill be recognized by those skilled) in forming the benzofurano-fusednaphthopyrans, indolo-fused naphthopyrans and/or benzothieno-fusednaphthopyrans according to various non-limiting embodiments disclosedherein are set forth in U.S. Pat. No. 5,651,923 at col. 6, line 43 tocol. 13, line 48, which disclosure is hereby specifically incorporatedby reference herein; U.S. Pat. No. 6,018,059 at column 6, line 1 tocolumn 7, line 64, which disclosure is hereby specifically incorporatedby reference herein; and U.S. Pat. No. 6,392,043 at column 6, line 5 tocolumn 10, line 10, which disclosure is hereby specifically incorporatedby reference herein.

In an embodiment of the present invention, the photochromic material ofthe present invention, including the indeno-fused naphthopyrans asdescribed, for example, with reference to FIGS. 1 and/or 2, displayshyperchromic absorption of electromagnetic radiation having a wavelengthfrom 320 nm to 420 nm, as compared to a comparative photochromicmaterial comprising a comparable indeno-fused naphthopyran that issubstantially free of the pi-conjugation extending group bonded to the11-position of the comparable indeno-fused naphthopyran. As used hereinand in the claims, the term “hyperchromic absorption” refers to anincrease in the absorption of electromagnetic radiation by aphotochromic material having a pi-conjugation extending group (e.g., asdescribed with reference to R^(a)) bonded to the 11-position of theindeno-fused naphthopyran, on a per molecule basis as compared to acomparable photochromic material that does not have a pi-conjugationextending group bonded to the 11-position of the comparable indeno-fusednaphthopyran.

The present invention also relates to an optical element that includesone or more indeno-fused naphthopyrans according to the presentinvention. In particular, the optical element that includes one or moreindeno-fused naphthopyrans that includes: a pi-conjugation extendinggroup bonded to the 11-position of the indeno-fused, the pi-conjugationextending group having at least one pendent halo-substituted groupbonded thereto, the pi-conjugation extending group extending thepi-conjugation system of the indeno-fused naphthopyran; an ether groupbonded to the 6 or 7-position of the indeno-fused naphthopyran, theether-oxygen of the ether group being bonded to the 6 or 7-position;and/or an amino group bonded to the 6 or 7-position of the indeno-fusednaphthopyran, the amine-nitrogen of said amino group being bonded to the6 or 7-position, the amino group being selected from secondary amines ortertiary amines. The 13-position of the indeno-fused naphthopyran,incorporated into the optical element, is substantially free ofspiro-substituents. Optical elements that may include the photochromicmaterials, including the indeno-fused naphthopyrans, of the presentinvention are described in further detail herein below. As discussedabove, the photochromic materials according to various non-limitingembodiments disclosed herein may be incorporated into at least a portionof an organic material, such as a polymeric, oligomeric or monomericmaterial to form a photochromic composition, which may be used, forexample and without limitation, to form photochromic articles, such asoptical elements, and coating compositions that may be applied tovarious substrates. As used herein the terms “polymer” and “polymericmaterial” refer to homopolymers and copolymers (e.g., random copolymers,block copolymers, and alternating copolymers), as well as blends andother combinations thereof. As used herein the terms “oligomer” and“oligomeric material” refer to a combination of two or more monomerunits that is capable of reacting with additional monomer unit(s). Asused herein the term “incorporated into” means physically and/orchemically combined with. For example, the photochromic materialsaccording to various non-limiting embodiments disclosed herein may bephysically combined with at least a portion of an organic material, forexample and without limitation, by mixing or imbibing the photochromicmaterial into the organic material; and/or chemically combined with atleast a portion of an organic material, for example and withoutlimitation, by copolymerization or otherwise bonding the photochromicmaterial to the organic material.

Further, it is contemplated that the photochromic materials according tovarious non-limiting embodiments disclosed herein may each be usedalone, in combination with other photochromic materials according tovarious non-limiting embodiments disclosed herein, or in combinationwith an appropriate complementary conventional photochromic material.For example, the photochromic materials according to variousnon-limiting embodiments disclosed herein may be used in conjunctionwith conventional photochromic materials having activated absorptionmaxima within the range of 300 to 1000 nanometers. Further, thephotochromic materials according to various non-limiting embodimentsdisclosed herein may be used in conjunction with a complementaryconventional polymerizable or a compatiblized photochromic material,such as for example, those disclosed in U.S. Pat. Nos. 6,113,814 (atcol. 2, line 39 to col. 8, line 41), and 6,555,028 (at col. 2, line 65to col. 12, line 56), which disclosures are hereby specificallyincorporated by reference herein.

As discussed above, according to various non-limiting embodimentsdisclosed herein, the photochromic compositions may contain a mixture ofphotochromic materials. For example, although not limiting herein,mixtures of photochromic materials may be used to attain certainactivated colors such as a near neutral gray or near neutral brown. See,for example, U.S. Pat. No. 5,645,767, col. 12, line 66 to col. 13, line19, which describes the parameters that define neutral gray and browncolors and which disclosure is specifically incorporated by referenceherein.

Various non-limiting embodiments disclosed herein provide a photochromiccomposition comprising an organic material, said organic material beingat least one of polymeric material, an oligomeric material and amonomeric material, and a photochromic material according to any of thenon-limiting embodiments of set forth above incorporated into at least aportion of the organic material. According to various non-limitingembodiments disclosed herein, the photochromic material may beincorporated into a portion of the organic material by at least one ofblending and bonding the photochromic material with the organic materialor a precursor thereof. As used herein with reference to theincorporation of photochromic materials into an organic material, theterms “blending” and “blended” mean that the photochromic material isintermixed or intermingled with the at least a portion of the organicmaterial, but not bonded to the organic material. Further, as usedherein with reference to the incorporation of photochromic materialsinto an organic material, the terms “bonding” or “bonded” mean that thephotochromic material is linked to a portion of the organic material ora precursor thereof. For example, although not limiting herein, thephotochromic material may be linked to the organic material through areactive substituent.

According to one non-limiting embodiment wherein the organic material isa polymeric material, the photochromic material may be incorporated intoat least a portion of the polymeric material or at least a portion ofthe monomeric material or oligomeric material from which the polymericmaterial is formed. For example, photochromic materials according tovarious non-limiting embodiments disclosed herein that have a reactivesubstituent may be bonded to an organic material such as a monomer,oligomer, or polymer having a group with which a reactive moiety may bereacted, or the reactive moiety may be reacted as a co-monomer in thepolymerization reaction from which the organic material is formed, forexample, in a co-polymerization process.

As discussed above, the photochromic compositions according to variousnon-limiting embodiments disclosed herein may comprise an organicmaterial chosen from a polymeric material, an oligomeric material and/ora monomeric material. Examples of polymeric materials that may be usedin conjunction with various non-limiting embodiments disclosed hereininclude, without limitation: polymers of bis(allyl carbonate) monomers;diethylene glycol dimethacrylate monomers; diisopropenyl benzenemonomers; ethoxylated bisphenol A dimethacrylate monomers; ethyleneglycol bismethacrylate monomers; poly(ethylene glycol) bismethacrylatemonomers; ethoxylated phenol bismethacrylate monomers; alkoxylatedpolyhydric alcohol acrylate monomers, such as ethoxylated trimethylolpropane triacrylate monomers; urethane acrylate monomers; vinylbenzenemonomers; and styrene. Other non-limiting examples of suitable polymericmaterials include polymers of polyfunctional, e.g., mono-, di- ormulti-functional, acrylate and/or methacrylate monomers; poly(C₁-C₁₂alkyl methacrylates), such as poly(methyl methacrylate);poly(oxyalkylene)dimethacrylate; poly(alkoxylated phenol methacrylates);cellulose acetate; cellulose triacetate; cellulose acetate propionate;cellulose acetate butyrate; poly(vinyl acetate); poly(vinyl alcohol);poly(vinyl chloride); poly(vinylidene chloride); polyurethanes;polythiourethanes; thermoplastic polycarbonates; polyesters;poly(ethylene terephthalate); polystyrene; poly(□-methylstyrene);copolymers of styrene and methyl methacrylate; copolymers of styrene andacrylonitrile; polyvinylbutyral; and polymers of diallylidenepentaerythritol, particularly copolymers with polyol (allyl carbonate)monomers, e.g., diethylene glycol bis(allyl carbonate), and acrylatemonomers, e.g., ethyl acrylate, butyl acrylate. Also contemplated arecopolymers of the aforementioned monomers, combinations, and blends ofthe aforementioned polymers and copolymers with other polymers, e.g., toform interpenetrating network products.

Further, according to various non-limiting embodiments whereintransparency of the photochromic composition is desired, the organicmaterial may be a transparent polymeric material. For example, accordingto various non-limiting embodiments, the polymeric material may be anoptically clear polymeric material prepared from a thermoplasticpolycarbonate resin, such as the resin derived from bisphenol A andphosgene, which is sold under the trademark, LEXAN®; a polyester, suchas the material sold under the trademark, MYLAR®; a poly(methylmethacrylate), such as the material sold under the trademark,PLEXIGLAS®; and polymerizates of a polyol(allyl carbonate) monomer,especially diethylene glycol bis(allyl carbonate), which monomer is soldunder the trademark CR-39®; and polyurea-polyurethane (polyureaurethane) polymers, which are prepared, for example, by the reaction ofa polyurethane oligomer and a diamine curing agent, a composition forone such polymer being sold under the trademark TRIVEX® by PPGIndustries, Inc. Other non-limiting examples of suitable polymericmaterials include polymerizates of copolymers of a polyol (allylcarbonate), e.g., diethylene glycol bis(allyl carbonate), with othercopolymerizable monomeric materials, such as, but not limited to:copolymers with vinyl acetate, copolymers with a polyurethane havingterminal diacrylate functionality, and copolymers with aliphaticurethanes, the terminal portion of which contain allyl or acrylylfunctional groups. Still other suitable polymeric materials include,without limitation, poly(vinyl acetate), polyvinylbutyral, polyurethane,polythiourethanes, polymers chosen from diethylene glycol dimethacrylatemonomers, diisopropenyl benzene monomers, ethoxylated bisphenol Adimethacrylate monomers, ethylene glycol bismethacrylate monomers,poly(ethylene glycol) bismethacrylate monomers, ethoxylated phenolbismethacrylate monomers and ethoxylated trimethylol propane triacrylatemonomers, cellulose acetate, cellulose propionate, cellulose butyrate,cellulose acetate butyrate, polystyrene and copolymers of styrene withmethyl methacrylate, vinyl acetate and acrylonitrile. According to onenon-limiting embodiment, the polymeric material may be an optical resinssold by PPG Industries, Inc. under the CR-designation, e.g., CR-307,CR-407, and CR-607.

According to one specific non-limiting embodiment, the organic materialmay be a polymeric material which is chosen from poly(carbonate),copolymers of ethylene and vinyl acetate; copolymers of ethylene andvinyl alcohol; copolymers of ethylene, vinyl acetate, and vinyl alcohol(such as those that result from the partial saponification of copolymersof ethylene and vinyl acetate); cellulose acetate butyrate;poly(urethane); poly(acrylate); poly(methacrylate); epoxies; aminoplastfunctional polymers; poly(anhydride); poly(urea urethane);N-alkoxymethyl(meth)acrylamide functional polymers; poly(siloxane);poly(silane); and combinations and mixtures thereof.

As previously discussed, it has been observed by the inventors that thephotochromic materials according to certain non-limiting embodimentsdisclosed herein may display hyperchromic absorption of electromagneticradiation having a wavelength from 320 nm to 420 nm as compared to aphotochromic materials comprising a comparable indeno-fused naphthopyranwithout the group that extends the pi-conjugated system (having at leastone pendant halo-substituted group bonded thereto) of the comparableindeno-fused naphthopyran bonded at the 11-position thereof.Accordingly, photochromic compositions comprising the photochromicmaterials according to various non-limiting embodiments disclosed hereinmay also displays increased absorption of electromagnetic radiationhaving a wavelength from 320 nm to 420 nm as compared to a photochromiccomposition comprising a comparable indeno-fused naphthopyran withoutthe group that extends the pi-conjugated system of the comparableindeno-fused naphthopyran bonded at the 11-position thereof.

Additionally, as previously discussed, since the photochromic materialsaccording to certain non-limiting embodiments disclosed herein maydisplay hyperchromic properties as discussed above, it is contemplatedthat the amount or concentration of the photochromic material present inphotochromic compositions according to various non-limiting embodimentsdisclosed herein may be reduced as compared to the amount orconcentration of a conventional photochromic materials that is typicallyrequired to achieve a desired optical effect. Since it may be possibleto use less of the photochromic materials according to certainnon-limiting embodiments disclosed herein than conventional photochromicmaterials while still achieving the desired optical effects, it iscontemplated that the photochromic materials according to variousnon-limiting embodiments disclosed herein may be advantageously employedin applications wherein it is necessary or desirable to limit the amountof photochromic material used.

Further, as previously discussed, it has been observed by the inventorsthat the photochromic materials according to certain non-limitingembodiments disclosed herein the may have a closed-form absorptionspectrum for electromagnetic radiation having a wavelength ranging from320 nm to 420 nm that is bathochromically shifted as compared to aclosed-form absorption spectrum for electromagnetic radiation having awavelength ranging from 320 nm to 420 nm of a photochromic materialcomprising a comparable indeno-fused naphthopyran without the grouphaving a pendant halo-substituted group that extends the pi-conjugatedsystem of comparable the indeno-fused naphthopyran bonded at the11-position thereof. Accordingly, photochromic compositions comprise thephotochromic materials according to various non-limiting embodimentsdisclosed herein may also have an absorption spectrum forelectromagnetic radiation having a wavelength ranging from 320 nm to 420nm that is bathochromically shifted as compared to an absorptionspectrum for electromagnetic radiation having a wavelength ranging from320 nm to 420 nm of a photochromic composition comprising a comparableindeno-fused naphthopyran without the group having a pendanthalo-substituted group that extends the pi-conjugated system of thecomparable indeno-fused naphthopyran bonded at the 11-position thereof.

As previously discussed, the present invention further contemplatesphotochromic articles, such as optical elements, made using thephotochromic materials and compositions according to variousnon-limiting embodiments disclosed herein. As used herein the term“optical” means pertaining to or associated with light and/or vision.The optical elements according to various non-limiting embodimentsdisclosed herein may include, without limitation, ophthalmic elements,display elements, windows, mirrors, and liquid crystal cell elements. Asused herein the term “ophthalmic” means pertaining to or associated withthe eye and vision. Non-limiting examples of ophthalmic elements includecorrective and non-corrective lenses, including single vision ormulti-vision lenses, which may be either segmented or non-segmentedmulti-vision lenses (such as, but not limited to, bifocal lenses,trifocal lenses and progressive lenses), as well as other elements usedto correct, protect, or enhance (cosmetically or otherwise) vision,including without limitation, magnifying lenses, protective lenses,visors, goggles, as well as, lenses for optical instruments (forexample, cameras and telescopes). As used herein the term “display”means the visible or machine-readable representation of information inwords, numbers, symbols, designs or drawings. Non-limiting examples ofdisplay elements include screens, monitors, and security elements, suchas security marks. As used herein the term “window” means an apertureadapted to permit the transmission of radiation therethrough.Non-limiting examples of windows include automotive and aircrafttransparencies, windshields, filters, shutters, and optical switches. Asused herein the term “mirror” means a surface that specularly reflects alarge fraction of incident light. As used herein the term “liquidcrystal cell” refers to a structure containing a liquid crystal materialthat is capable of being ordered. One non-limiting example of a liquidcrystal cell element is a liquid crystal display.

Various non-limiting embodiments disclosed herein provide photochromicarticles, such as optical elements, comprising a substrate and aphotochromic material according to any of the non-limiting embodimentsdiscussed above connected to a portion of the substrate. As used herein,the term “connected to” means associated with, either directly orindirectly through another material or structure.

According to various non-limiting embodiments disclosed herein whereinthe substrate of the photochromic article comprises a polymericmaterial, the photochromic material may be connected to at least aportion of the substrate by incorporating the photochromic material intoat least a portion of the polymeric material of the substrate, or byincorporating the photochromic material into at least a portion of theoligomeric or monomeric material from which the substrate is formed. Forexample, according to one non-limiting embodiment, the photochromicmaterial may be incorporated into the polymeric material of thesubstrate by the cast-in-place method or by imbibition. Imbibition andthe cast-in-place method are discussed below.

According to still other non-limiting embodiments, the photochromicmaterial may be connected to at least a portion of the substrate of thephotochromic article as part of at least partial coating that isconnected to at least a portion of a substrate. According to thisnon-limiting embodiment, the substrate may be a polymeric substrate oran inorganic substrate (such as, but not limited to, a glass substrate).Further, the photochromic material may be incorporated into at least aportion of a coating composition prior to application of the coatingcomposition to the substrate, or alternatively, a coating compositionmay be applied to the substrate, at least partially set, and thereafterthe photochromic material may be imbibed into at least a portion of thecoating. As used herein, the terms “set” and “setting” include, withoutlimitation, curing, polymerizing, cross-linking, cooling, and drying.

The at least partial coating comprising the photochromic material may beconnected to at least a portion of the substrate, for example, byapplying a coating composition comprising the photochromic material toat least a portion of a surface of the substrate, and at least partiallysetting the coating composition. Additionally or alternatively, the atleast partial coating comprising the photochromic material may beconnected to the substrate, for example, through one or more additionalat least partial coatings. For example, while not limiting herein,according to various non-limiting embodiments, an additional coatingcomposition may be applied to a portion of the surface of the substrate,at least partially set, and thereafter the coating compositioncomprising the photochromic material may be applied over the additionalcoating and at least partially set. Non-limiting methods of applyingcoatings compositions to substrates are discussed herein below.

Non-limiting examples of additional coatings and films that may be usedin conjunction with the photochromic articles disclosed herein includeprimer coatings and films; protective coatings and films, includingtransitional coatings and films and abrasion resistant coatings andfilms; anti-reflective coatings and films; conventional photochromiccoating and films; and polarizing coatings and films; and combinationsthereof. As used herein the term “protective coating or film” refers tocoatings or films that can prevent wear or abrasion, provide atransition in properties from one coating or film to another, protectagainst the effects of polymerization reaction chemicals and/or protectagainst deterioration due to environmental conditions such as moisture,heat, ultraviolet light, oxygen, etc.

Non-limiting examples of primer coatings and films that may be used inconjunction with various non-limiting embodiments disclosed hereininclude coatings and films comprising coupling agents, at least partialhydrolysates of coupling agents, and mixtures thereof. As used herein“coupling agent” means a material having a group capable of reacting,binding and/or associating with a group on a surface. Coupling agentsaccording to various non-limiting embodiments disclosed herein mayinclude organometallics such as silanes, titanates, zirconates,aluminates, zirconium aluminates, hydrolysates thereof and mixturesthereof. As used herein the phrase “at least partial hydrolysates ofcoupling agents” means that some to all of the hydrolyzable groups onthe coupling agent are hydrolyzed. Other non-limiting examples of primercoatings that are suitable for use in conjunction with the variousnon-limiting embodiments disclosed herein include those primer coatingsdescribed U.S. Pat. No. 6,025,026 at col. 3, line 3 to col. 11, line 40and U.S. Pat. No. 6,150,430 at col. 2, line 39 to col. 7, line 58, whichdisclosures are hereby specifically incorporated herein by reference.

As used herein, the term “transitional coating and film” means a coatingor film that aids in creating a gradient in properties between twocoatings or films, or a coating and a film. For example, although notlimiting herein, a transitional coating may aid in creating a gradientin hardness between a relatively hard coating and a relatively softcoating. Non-limiting examples of transitional coatings includeradiation-cured, acrylate-based thin films as described in U.S. PatentApplication Publication 2003/0165686 at paragraphs 79-173, which arehereby specifically incorporated by reference herein.

As used herein the term “abrasion resistant coating and film” refers toa protective polymeric material that demonstrates a resistance toabrasion that is greater than a standard reference material, e.g., apolymer made of CR-39® monomer available from PPG industries, Inc, astested in a method comparable to ASTM F-735 Standard Test Method forAbrasion Resistance of Transparent Plastics and Coatings Using theOscillating Sand Method. Non-limiting examples of abrasion resistantcoatings include abrasion-resistant coatings comprising organosilanes,organosiloxanes, abrasion-resistant coatings based on inorganicmaterials such as silica, titania and/or zirconia, organicabrasion-resistant coatings of the type that are ultraviolet lightcurable, oxygen barrier-coatings, UV-shielding coatings, andcombinations thereof.

Non-limiting examples of antireflective coatings and films include amonolayer, multilayer or film of metal oxides, metal fluorides, or othersuch materials, which may be deposited onto the articles disclosedherein (or onto films that are applied to the articles), for example,through vacuum deposition, sputtering, etc. Non-limiting examples ofconventional photochromic coatings and films include, but are notlimited to, coatings and films comprising conventional photochromicmaterials. Non-limiting examples of polarizing coatings and filmsinclude, but are not limited to, coatings and films comprising dichroiccompounds that are known in the art.

As discussed above, according to various non-limiting embodiments, anadditional at least partial coating or film may be formed on thesubstrate prior to forming the coating comprising the photochromicmaterial according to various non-limiting embodiments disclosed hereinon the substrate. For example, according to certain non-limitingembodiments a primer coating may be formed on the substrate prior toapplying the coating composition comprising the photochromic material.Additionally or alternatively, the additional at least partial coatingor film may be formed on the substrate after forming coating comprisingthe photochromic material according to various non-limiting embodimentsdisclosed herein on the substrate, for example, as an overcoating. Forexample, according to certain non-limiting embodiments, a transitionalcoating may be formed over the coating comprising the photochromicmaterial, and an abrasion resistant coating may be formed over thetransitional coating.

Another non-limiting embodiment provides an optical element adapted foruse behind a substrate that blocks a substantial portion ofelectromagnetic radiation in the range of 320 nm to 390 nm, the opticalelement comprising a photochromic material comprising an indeno-fusednaphthopyran and a group that extends the pi-conjugated system of theindeno-fused naphthopyran bonded at the 11-position thereof connected toat least a portion of the optical element, wherein the at least aportion of the optical element absorbs a sufficient amount ofelectromagnetic radiation having a wavelength greater than 390 nmpassing through the substrate that blocks a substantial portion ofelectromagnetic radiation in the range of 320 nm to 390 nm such that theat least a portion of the optical element transforms from a first stateto a second state. For example, according to this non-limitingembodiment, the first state may be a bleached state and the second statemay be a colored state that corresponds to the colored state of thephotochromic material(s) incorporated therein.

As previously discussed, many conventional photochromic materialsrequire electromagnetic radiation having a wavelength ranging from 320nm to 390 nm to cause the photochromic material to transformation from aclosed-form to an open-form (e.g., from a bleached state to a coloredstate). Therefore, conventional photochromic materials may not achievetheir fully-colored state when use in applications that are shieldedfrom a substantial amount of electromagnetic radiation in the range of320 nm to 390 nm. Further, as previous discussed, it has been observedby the inventors that photochromic material according to certainnon-limiting embodiments disclosed herein may display both hyperchromicand bathochromic properties. That is, the indeno-fused naphthopyranscomprising a group that extends the pi-conjugated system of theindeno-fused naphthopyran at the 11-position thereof according tocertain non-limiting embodiments disclosed herein may not only displayhyperchromic absorption of electromagnetic radiation as discussed above,but may also have a closed-form absorption spectrum for electromagneticradiation having a wavelength ranging from 320 nm to 420 nm that isbathochromically shifted as compared to a closed-form absorptionspectrum for electromagnetic radiation having a wavelength ranging from320 nm to 420 nm of a comparable indeno-fused naphthopyran without thegroup that extends the pi-conjugated system of the comparableindeno-fused naphthopyran bonded at the 11-position thereof.Accordingly, the photochromic materials according to certainnon-limiting embodiments disclosed herein may absorb a sufficient amountof electromagnetic radiation passing through a substrate that blocks asubstantial portion of electromagnetic radiation having a wavelengthranging from 320 to 390 nm such that the photochromic material maytransform from a closed-form to an open-form. That is, the amount ofelectromagnetic radiation having a wavelength of greater than 390 nmthat is absorbed by the photochromic materials according to variousnon-limiting embodiments disclosed herein may be sufficient to permitthe photochromic materials to transform from a closed-form to anopen-form, thereby enabling their use behind a substrate that blocks asubstantial portion of electromagnetic radiation having a wavelengthranging from 320 nm to 390 nm.

Non-limiting methods of making photochromic compositions andphotochromic articles, such as optical elements, according to variousnon-limiting embodiments disclosed herein will now be discussed. Onenon-limiting embodiment provides a method of making a photochromiccomposition, the method comprising incorporating a photochromic materialinto at least a portion of an organic material. Non-limiting methods ofincorporating photochromic materials into an organic material include,for example, mixing the photochromic material into a solution or melt ofa polymeric, oligomeric, or monomeric material, and subsequently atleast partially setting the polymeric, oligomeric, or monomeric material(with or without bonding the photochromic material to the organicmaterial); and imbibing the photochromic material into the organicmaterial (with or without bonding the photochromic material to theorganic material).

Another non-limiting embodiment provides a method of making aphotochromic article comprising connecting a photochromic materialaccording to various non-limiting embodiments discussed above, to atleast a portion a substrate. For example, if the substrate comprises apolymeric material, the photochromic material may be connected to atleast a portion of the substrate by at least one of the cast-in-placemethod and by imbibition. For example, in the cast-in-place method, thephotochromic material may be mixed with a polymeric solution or melt, orother oligomeric and/or monomeric solution or mixture, which issubsequently cast into a mold having a desired shape and at leastpartially set to form the substrate, Optionally, according to thisnon-limiting embodiment, the photochromic material may be bonded to aportion of the polymeric material of the substrate, for example, byco-polymerization with a monomeric precursor thereof. In the imbibitionmethod, the photochromic material may be diffuse into the polymericmaterial of the substrate after it is formed, for example, by immersinga substrate in a solution containing the photochromic material, with orwithout heating. Thereafter, although not required, the photochromicmaterial may be bonded with the polymeric material.

Other non-limiting embodiments disclosed herein provide a method ofmaking an optical element comprising connecting a photochromic materialto at least a portion of a substrate by at least one of in-mold casting,coating and lamination. For example, according to one non-limitingembodiment, wherein the substrate comprises a polymeric material, thephotochromic material may be connected to at least a portion of asubstrate by in-mold casting. According to this non-limiting embodiment,a coating composition comprising the photochromic material, which may bea liquid coating composition or a powder coating composition, is appliedto the surface of a mold and at least partially set. Thereafter, apolymer solution or melt, or oligomeric or monomeric solution or mixtureis cast over the coating and at least partially set. After setting, thecoated substrate is removed from the mold. Non-limiting examples ofpowder coatings in which the photochromic materials according to variousnon-limiting embodiments disclosed herein may be employed are set forthin U.S. Pat. No. 6,068,797 at col. 7, line 50 to col. 19, line 42, whichdisclosure is hereby specifically incorporated by reference herein.

According to still another non-limiting embodiment, wherein thesubstrate comprises a polymeric material or an inorganic material suchas glass, the photochromic material may be connected to at least aportion of a substrate by coating. Non-limiting examples of suitablecoating methods include spin coating, spray coating (e.g., using aliquid or powder coating), curtain coating, roll coating, spin and spraycoating, over-molding, and combinations thereof. For example, accordingto one non-limiting embodiment, the photochromic material may beconnected to the substrate by over-molding. According to thisnon-limiting embodiment, a coating composition comprising thephotochromic material (which may be a liquid coating composition or apowder coating composition as previously discussed) may be applied to amold and then the substrate may be placed into the mold such that thesubstrate contacts the coating causing it to spread over at least aportion of the surface of the substrate. Thereafter, the coatingcomposition may be at least partially set and the coated substrate maybe removed from the mold. Alternatively, over-molding may be done byplacing the substrate into a mold such that an open region is definedbetween the substrate and the mold, and thereafter injecting a coatingcomposition comprising the photochromic material into the open region.Thereafter, the coating composition may be at least partially set andthe coated substrate may be removed from the mold.

Additionally or alternatively, a coating composition (with or without aphotochromic material) may be applied to a substrate (for example, byany of the foregoing methods), the coating composition may be at leastpartially set, and thereafter, a photochromic material may be imbibed(as previously discussed) into the coating composition.

According to yet another non-limiting embodiment, wherein the substratecomprises a polymeric material or an inorganic material such as glass,the photochromic material may be connected to at least a portion of asubstrate by lamination. According to this non-limiting embodiment, afilm comprising the photochromic material may be adhered or otherwiseconnect to a portion of the substrate, with or without an adhesiveand/or the application of heat and pressure. Thereafter, if desired, asecond substrate may be applied over the first substrate and the twosubstrates may be laminated together (i.e., by the application of heatand pressure) to form an element wherein the film comprising thephotochromic material is interposed between the two substrates. Methodsof forming films comprising a photochromic material may include forexample and without limitation, combining a photochromic material with apolymeric solution or oligomeric solution or mixture, casting orextruding a film therefrom, and, if required, at least partially settingthe film. Additionally or alternatively, a film may be formed (with orwithout a photochromic material) and imbibed with the photochromicmaterial (as discussed above).

Further, various non-limiting embodiments disclosed herein contemplatethe use of various combinations of the foregoing methods to formphotochromic articles according to various non-limiting embodimentsdisclosed herein. For example, and without limitation herein, accordingto one non-limiting embodiment, a photochromic material may be connectedto substrate by incorporation into an organic material from which thesubstrate is formed (for example, using the cast-in-place method and/orimbibition), and thereafter a photochromic material (which may be thesame or different from the aforementioned photochromic material) may beconnected to a portion of the substrate using the in-mold casting,coating and/or lamination methods discussed above.

Further, it will be appreciated by those skilled in the art that thephotochromic compositions and articles according to various non-limitingembodiments disclosed herein may further comprise other additives thataid in the processing and/or performance of the composition or article.Non-limiting examples of such additives include from photoinitiators,thermal initiators, polymerization inhibitors, solvents, lightstabilizers (such as, but not limited to, ultraviolet light absorbersand light stabilizers, such as hindered amine light stabilizers (HALS)),heat stabilizers, mold release agents, rheology control agents, levelingagents (such as but not limited to, surfactants), free radicalscavengers, adhesion promoters (such as hexanediol diacrylate andcoupling agents), and combinations and mixtures thereof.

According to various non-limiting embodiments, the photochromicmaterials described herein may be used in amounts (or ratios) such thatthe organic material or substrate into which the photochromic materialsare incorporated or otherwise connected exhibits desired opticalproperties. For example, the amount and types of photochromic materialsmay be selected such that the organic material or substrate may be clearor colorless when the photochromic material is in the closed-form (i.e.,in the bleached or unactivated state) and may exhibit a desiredresultant color when the photochromic material is in the open-form (thatis, when activated by actinic radiation). The precise amount of thephotochromic material to be utilized in the various photochromiccompositions and articles described herein is not critical provided thata sufficient amount is used to produce the desired effect. It should beappreciated that the particular amount of the photochromic material usedmay depend on a variety of factors, such as but not limited to, theabsorption characteristics of the photochromic material, the color andintensity of the color desired upon activation, and the method used toincorporate or connect the photochromic material to the substrate.Although not limiting herein, according to various non-limitingembodiments disclosed herein, the amount of the photochromic materialthat is incorporated into an organic material may range from 0.01 to 40weight percent based on the weight of the organic material.

Various non-limiting embodiments disclosed herein will now beillustrated in the following non-limiting examples.

EXAMPLES

In Part 1 of the Examples, the synthesis procedures used to makephotochromic materials according to various non-limiting embodimentsdisclosed herein are set forth in Examples 1-13, and the procedures usedto make the comparative photochromic materials are described inComparative Examples (CE) 1-10. In Part 2, the photochromic performancetesting is described. In Part 3, the test results are reported.

Part 1—Photochromic Materials—Synthesis Example 1

Step 1

Into a 3 liter reaction (3 neck) flask was added2,3-dimethoxy-7,7-dimethyl-9-bromo-7H-benzo[C]fluoren-5-ol (170 grams)the product of Step 5 of Example 1 in U.S. Patent Publication2006-0228557, which disclosure is incorporated herein by reference,4-trifluoromethyl phenyl boronic acid (100 g), Na₂CO₃(93 g),1,2-dimethoxyethane (1 L), water (500 mL). Nitrogen was bubbled throughthe reaction mixture for 15 minutes. Tetrakis (triphenylphosphine)palladium (0) (15.2 g) was added to the reaction mixture and theresulting reaction mixture was heated to reflux and maintained at refluxovernight. The reaction mixture was cooled to room temperature and HCl(37%, 97 g) was added slowly. The reaction mixture separated and theproduct was extracted from the aqueous layer with ethyl acetate (EtOAc).The EtOAc layer was dried over MgSO₄, and concentrated under vacuum toprovide viscous oil. The oil was slurried in a mixture of EtOAc andhexane (70/30 volume ratio) and the resulting solid was filtered toprovide 170 g of product. Approximately one-half of the product wasfurther slurried in the mixture of EtOAc and hexane (70/30 volumeratio), and then filtered and washed with dichloromethane to provide ayellow solid (40 g). The purified product was used as is for next step.

Step 2

Into a 250 mL reaction flask was added the product of Step 1, (4.0 g),1,1-bis(4-methoxyphenyl)-2-propyn-1-ol (2.43 g), and chloroform (125mL). To the resulting reaction mixture was added 0.25 grams of PPTS(pyridinium p-toluene-sulfonate). The reaction mixture was stirred atroom temperature for 2 hours and further additions of1,1-bis(4-methoxyphenyl)-2-propyn-1-ol (0.25 g) and PPTS (0.05 g) weremade. The reaction mixture was stirred for another 2 hours and thenwashed with 200 mL of a 1:1 mixture of saturated aqueous NaHCO₃ andwater. After the resulting layers separated, the organic layer wasrecovered, dried over anhydrous sodium sulfate and concentrated byrotary evaporation. The resulting residue was purified by slurrying in a1:1 mixture of acetone and diethyl ether. An off-white solid resultedand was collected by filtration to yield 4.1 grams of product. NMRanalysis showed the product to have a structure consistent with3,3-di(4-methoxyphenyl)-6,7-dimethoxy-1′-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 2

Step 1

Into a suitable reaction flask was added2,3-dimethoxy-7,7-dimethyl-9-bromo-7H-benzo[C]fluoren-5-ol (13.3 g),3,5-bis(trifluoromethyl)phenylboronic acid (12.0 g), K₂CO₃ (14.0 g),triphenylphosphine (3.4 g), 1,2-dimethoxyethane (400 mL), and water (200mL). Nitrogen was bubbled through the reaction mixture for 10 minutes.Palladium II acetate (0.56 g) was added to the reaction mixture and theinitially orange colored solution turned dark before becoming orangeupon heating to reflux. After 3 hours of heating, the reaction wascooled to room temperature and the aqueous phase separated. Therecovered organic phase was diluted with dichloromethane and washedtwice with brine before drying over MgSO₄ and evaporating the solvent.The resulting residue was chromatographed on a short silica gel column,eluting with 10% EtOAc in dichloromethane. Product containing fractionswere combined and evaporated until the product began to crystallize.Hexane was added and the resulting solid was collected by filtration togive 16.5 g of tannish brown solid. This solid was used as is for thenext reaction.

Step 2

The product of Step 1 (6 g) and 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol(4 g) were combined in a round bottom flask and dissolved in chloroform(150 mL). To this solution, PPTS (0.15 g) was added. The reaction turneddark immediately and was heated to reflux for 2 hours. The solution wascooled to room temperature before being applied directly to a silica gelcolumn. Product containing fractions were combined and concentrateduntil crystallization began. A portion of hexanes was then added tofurther induce crystallization. The product (5.0 g) was collected byfiltration. NMR analysis showed the product to have a structureconsistent with3,3-di(4-methoxyphenyl)-6,7-dimethoxy-11-(3,5-bis(trifluoromethyl)phenyl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 3

Step 1

Into a 1 L reaction flask was added1-(4-bromophenyl)-2-methoxycarbonyl-4-hydroxy-6,7-dimethoxynaphthalene(45 g) produced by following Steps 1-3 of Example 1, in U.S. PatentPublication 2006-0228557, which disclosure is incorporated herein byreference, except that the acetoxy group of the product of Step 3(1-(4-bromophenyl)-2-methoxycarbonyl-4-acetoxy-6,7-dimethoxynaphthalene)was converted to hydroxy using standard methanolysis conditions(refluxing for one hour in methanol containing 10% (volume to volume)concentrated (12M) hydrochloric acid); dimethoxyethane (300 mL) andwater (100 g) followed by the addition of 2-trifluoromethylphenylboronic acid (25 g) and Na₂CO₃ (23 g). Nitrogen was bubbled through theresulting slurry for 15 minutes. Tetrakistriphenyl phosphine palladium(0) (4 g) was added to the reaction mixture and heated to reflux. Afterabout 5-6 hours, the reaction was cooled to room temperature and water(50 mL) was added. The solution pH was adjusted to 5.0 by addition ofHCl (37%, 40 g). After the layers separated the organic layer wascollected. The aqueous layer was extracted with EtOAc (2 times, 50 mLeach time). The organic layers were combined, dried over anhydrousMgSO₄, and concentrated under vacuum to yield product containing methyl4-hydroxy-6,7-dimethoxy-1-(2′-(trifluoromethyl)[1,1′-biphenyl]-4-yl)-2-naphthoate,(70 g). The product was used for next step without purification.

Step 2

Ethyl magnesium chloride (EtMgCl) (20% by weight in dry tetrahydrofuran(dTHF), 210 mL) was added to a 1 L reaction flask under nitrogen. Theproduct of Step 1 (17.5% by weight in dTHF, 200 mL) was added toreaction mixture over 40 minutes at room temperature. The reaction wasexothermic and reaction temperature rose to 35° C. Upon completion ofthe addition, the resulting reaction mixture was stirred for 2 hours.More EtMgCl (20% by weight in dTHF, 75 mL) was added to mixture. Afterone hour, the resulting mixture was poured into an aqueous 10 weightpercent HCl solution. After the layers separated the organic layer wascollected. The aqueous layer was extracted with EtOAc (2 times, 40 mLeach time). The organic layers were combined, dried over anhydrousMgSO₄, and concentrated under vacuum to yield a product containing3-(3-hydroxypentan-3-yl)-6,7-dimethoxy-4-(2′-(trifluoromethyl)-[1,1′-biphenyl]-4-yl)naphthalen-1-ol(34 g). The product was used for next step as it is.

Step 3

The product of Step 2 (34 g) was added to xylene (400 mL) in a 500 mLreaction flask, followed by addition of DBSA (dodecylbenzenesulfonicacid, 4 g). The reaction mixture was heated to reflux and maintained atreflux over night. Solvent was removed to yield unpurified product (39g). The product was purified by column chromatography (EtOAc/hexanes,1/3, volume ratio) to yield 10 g of product. NMR analysis showed theproduct to have a structure consistent with7,7-diethyl-2,3-dimethoxy-9-(2-(trifluoromethyl)phenyl)-7H-benzo[c]fluoren-5-ol.

Step 4

Into a 100 mL reaction flask was added, the product of Step 3 (0.2 gdissolved in 40 mL of dichloromethane, PPTS (0.2 g) and1,1-bis(4-methoxyphenyl)-2-propyn-1-ol (1 g). The resulting reactionmixture was stirred at room temperature for 4 hours. The solvent wasremoved by evaporation to provide 2.9 grams of unpurified product. Theproduct was purified by column chromatography using EtOAc/hexanes, 1/3,volume ratio to yield 1.5 g of product. NMR analysis showed the productto have a structure consistent with3,3-bis(4-methoxyphenyl)-6,7-dimethoxy-11-(2-trifluoromethyl)phenyl-13,13-diethyl-3H-13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran

Example 4

Into a 250 mL dry reaction flask was added piperidine (0.95 grams) and100 mL of dTHF. The mixture was stirred under a nitrogen atmosphere atroom temperature. n-Butyl lithium (BuLi) (4.5 mL of 2.5 M in hexanes)was added dropwise to the reaction mixture over a 5-minute period. Thereaction mixture became warm and a little cloudy. The product of Example1 (4.0 g) was added in portions over a 5-minute period to the reactionmixture. The color of the reaction mixture turned deep brown. Theresulting solution was stirred at room temperature for 2 hours. Aftercooling to room temperature, the reaction mixture was poured into 200 mLof saturated NaCl solution. Extraction was done with two 200 mL portionsof EtOAc. The recovered organic layers were combined and washed withsaturated NaCl solution (300 mL) followed by drying over anhydroussodium sulfate. The solvents were removed by rotary evaporation to yieldbrown oil that foamed upon drying. The brown oil was purified by columnchromatography (20% EtOAc in hexanes as the eluant). The fractions werecollected, combined, evaporated, and dried under vacuum to recover 2.68grams of product which was crystallized from ether to obtain a lightyellow solid product. NMR analysis showed the product to have astructure consistent with3,3-di-(4-methoxyphenyl-6-methoxy-7-piperidino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 5

Into a 500 mL reaction flask was added the product of Step 1 of Example1 (10.0 g), 1(4-methoxyphenyl)-1-(4-morpholinophenyl)-2-propyn-1-ol(7.66 g) and chloroform (250 mL). To the reaction mixture was added PPTS(0.54 g) and the resulting reaction mixture was stirred at roomtemperature overnight. Afterwards,1(4-methoxyphenyl)-1-(4-morpholinophenyl)-2-propyn-1-ol (0.70 g) andPPTS (0.05 g) were added and the reaction mixture was stirred foranother 2 hours. The resulting reaction mixture was washed with 400 mLof a 1:1 mixture of saturated aqueous NaHCO₃ and water. The recoveredorganic layer was dried over anhydrous sodium sulfate and concentratedby rotary evaporation. The resulting residue was purified by slurryingin diethyl ether. A greenish solid formed and was collected by vacuumfiltration to yield 16.2 grams of product. NMR analysis showed theproduct to have a structure consistent with3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6,7-dimethoxy-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 6

Into a 250 mL dry reaction flask was added piperidine (1.1 g) and 120 mLof dTHF. The resulting mixture was stirred under a nitrogen atmosphereat room temperature. BuLi (5.2 mL of 2.5 M in hexanes) was addeddropwise to the reaction mixture over a 5-minute period. The reactionmixture became warm and a little cloudy. The product of Example 3 (5.0g) was added in portions over a 5-minute period to the reaction mixture.The color of the reaction mixture turned deep reddish brown. Theresulting solution was stirred at room temperature for 2 hours. Thereaction mixture was poured into 300 mL of saturated NaCl solution.Extraction was done with two 250 mL portions of EtOAc. The organiclayers were combined and washed with saturated NaCl solution (400 mL)followed by drying over anhydrous sodium sulfate. The solvents wereremoved by rotary evaporation to yield reddish brown oil that foamedupon drying. The product was purified by column chromatography (amixture of hexane (40%), methylene chloride (50%) and EtOAc (10%) as thestarting eluant). The fractions were combined, rotovaped, and driedunder vacuum to obtain 3.25 grams of product. NMR analysis showed theproduct to have a structure consistent with3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6-methoxy-7-piperidino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 7

Into a 500 mL dry reaction flask was added morpholine (2.26 g) and 150mL of dTHF. The reaction mixture was stirred under a nitrogen atmosphereat 0° C. BuLi (10.4 mL of 2.5 M in hexanes) was added dropwise to thereaction mixture over a 5-minute period. The reaction mixture became alittle cloudy. The product of Example 3 (8.0 g) was added in portionsover a 5-minute period to the reaction mixture. The color of thereaction mixture turned dark greenish gray. The cooling bath was removedand the resulting solution was stirred at room temperature for 2 hours.The reaction mixture was poured into 400 mL of saturated NaCl solution.Extraction was done with two 250 mL portions of EtOAc. The recoveredorganic layers were combined and washed with saturated NaCl solution(400 mL) followed by drying over anhydrous sodium sulfate. The solventswere removed by rotary evaporation to yield greenish gray oil thatfoamed upon drying. The material was purified by column chromatography(a mixture of hexane (40%), methylene chloride (30%) and EtOAc (30%) asthe starting eluant). The fractions were combined, concentrated byrotary evaporation, and dried under vacuum to obtain greenish gray oil.This oil was dissolved in a minimum amount of diethyl ether and theresulting solution was cooled in the freezer overnight to get a yellowsolid product. This solid was filtered and dried to obtain 5.87 grams ofproduct. NMR analysis showed the product to have a structure consistentwith3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6-methoxy-7-morpholino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 8

Step 1

Into a 1 liter reaction flask was added methylene chloride (500 mL),dihydroxybenzophenone (107 g) and 3,4-dihydro-2H-pyran (DHP, 105 g). Theresulting mixture was cooled to about 5° C. in an ice bath. PPTS (1.0 g)was added and the reaction mixture was stirred 1.5 hours at 5° C.Triethylamine (1.0 g) was added and the mixture was stirred for anadditional 10 min. The resulting mixture was filtered through basicalumina and concentrated to 219 g of residue by rotary evaporation.Heptanes (250 mL) were added, and the product solidified. The solid wasisolated, washed with 200 mL heptanes and dried under vacuum to provide175 g of the productbis(4-((tetrahydro-2H-pyran-2-yl)oxy)phenyl)methanone.

Step 2

The product of Step 1 (153 g) was added to a 1 L reaction flask with 230mL dimethyl formamide (DMF). The mixture was cooled to 1° C. and wasbubbled with acetylene gas for 20 min. A slurry of sodium acetylide (18%by weight in xylene/mineral oil from Aldrich, 215 g) was added all atonce at 3° C. A brief exotherm to 11° C. was observed. After thereaction mixture was stirred in ice for 3.5 hrs, a 10 weight percentsolution of NaCl was carefully added. During the phase separation,toluene (150 mL) was added. The recovered organic layer was washed witha 10 weight percent solution of NaCl (2 times with 145 mL each time).The resulting solution was filtered through a small alumina plug. Thefiltrate was concentrated by rotary evaporation to provide 227.5 g ofproduct. NMR analysis showed the product to have a structure consistentwith 1,1-bis[4-((ditetrahydro-2H-pyran-2-yl)oxy)phenyl]-2-propyn-1-ol.

Step 3

The product of Step 2 (7.2 g) and the product of Step 1 of Example 2(7.5 g) were combined in a round bottom flask and dissolved inchloroform (130 mL). To this solution, PPTS (a catalytic amount ˜200 mg)was added. The reaction was heated to reflux. After 5 hours of heating,methanol (25 mL) and an additional 200 mg portion of PPTS were added.Product began to precipitate out and was allowed to settle overnight.The fine precipitate was collected via vacuum filtration. Theprecipitate was re-suspended in a 1:1 mixture of acetone and methanoland heated to near reflux. The precipitate was allowed to settleovernight before again being collected by filtration to yield a beigesolid product which was dried under vacuum. NMR analysis showed theproduct to have a structure consistent with3,3-di(4-hydroxyphenyl)-6,7-dimethoxy-11-(3,5-bis(trifluoromethyl))phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 9

Into a 250 mL dry reaction flask was added morpholine (0.97 g) and 120mL of dTHF. The mixture was stirred under a nitrogen atmosphere at roomtemperature. BuLi (4.5 mL of 2.5 M in hexanes) was added dropwise to thereaction mixture over a 5-minute period. The reaction mixture becamewarm and a little cloudy. The product of Example 1 (4.0 g) was added inportions over a 5-minute period to the reaction mixture. The color ofthe reaction mixture turned deep brown. The resulting solution wasstirred at room temperature for 2 hours. BuLi (1 mL of 2.5 M in hexanes)was added to the reaction mixture and stirred for another 2 hours. Thereaction mixture was poured into 200 mL of saturated NaCl solution.Extraction was done with two 200 mL portions of EtOAc. The recoveredorganic layers were combined and washed with saturated NaCl solution(300 mL) followed by drying over anhydrous sodium sulfate. The solventswere removed by rotary evaporation to yield brown oil that foamed upondrying. This material was purified by crystallization from ether toobtain 3.40 grams of a light yellow solid product. NMR analysis showedthe product to have a structure consistent with3,3-di-(4-methoxyphenyl-6-methoxy-7-morpholino-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 10

Step 1

Into a 1 liter reaction flask was added2,3-dimethoxy-7,7-dimethyl-9-bromo-7H-benzo[C]fluoren-5-ol (20 grams)the product of Step 5 of Example 1 in U.S. Patent Publication2006-0228557, 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol (14.14 grams, 1.05equivalents) and chloroform (125 mL) To this was added PPTS (0.63 grams,0.05 equivalents) and the reaction mixture was stirred at roomtemperature for 2 hours. The reaction mixture was then washed with 400mL of a 1:1 mixture of saturated aqueous NaHCO₃ and water. The layersseparated and the recovered organic layer was dried over anhydroussodium sulfate and concentrated by rotary evaporation. The resultingresidue was purified by slurrying in diethyl ether. An off-white solidresulted and was collected by filtration to yield 31.1 of product. NMRanalysis showed the product to have a structure consistent with3,3-di(4-methoxyphenyl)-6,7-dimethoxy-11-bromo-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Step 2

The product of Step 1 (10 g) was added to a 1 L reaction flaskcontaining dimethoxyethane (200 mL) and water (100 mL), followed byaddition of 2-trifluoromethylphenyl boronic acid (3.5 g) and Na₂CO₃ (3.3g). Nitrogen was bubbled through the resulting slurry for 15 minutes,Tetrakistriphenyl phosphine palladium (0) (0.6 g) was added to reactionmixture and heated to reflux. After about 5-6 hours, the reaction wascooled to room temperature and water (30 mL) was added. The solution pHwas adjusted to 5 by addition of HCl (37%, 8 g). After the layersseparated, the organic layer was collected. The aqueous layer wasextracted with EtOAc (2 times, 30 mL each time). The organic layers werecombined, dried over anhydrous MgSO₄, and concentrated under vacuum toyield unpurified product (12 g). The product was purified by columnchromatography (EtOAc/Hexanes, 1/3, volume ratio) to yield3,3-bis(4-methoxyphenyl)-6,7-dimethoxy-11-(2-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran(8 g).

Step 3

Morpholine (0.7 g) was dissolved in dTHF (40 mL) in a 100 mL reactionflask. BuLi (2.5 M in hexanes, 2.7 mL) was added slowly. The resultedsolution was stirred at room temperature for 30 minutes and the productof Step 1 (1.6 g) was added slowly to the reaction mixture. After 1 hourof stirring at room temperature, morpholine (0.45 g) and BuLi (1.8 mL)were added to the reaction mixture in that order. After 30 minutes, thereaction was poured into water (50 mL). The product was extracted withEtOAc (2 times with 10 mL each time). The recovered organic layers werecombined, dried over anhydrous MgSO₄, and concentrated under vacuum toprovide product (2.0 g). The product was purified by columnchromatography (EtOAc/Hexanes, 1/3, volume ratio). The fractions wereconcentrated and the solid was slurried in methanol (MeOH). The slurrywas filtered via a fritted filter and washed with MeOH (3 times eachtime with 20 mL) to provide 1.1 g of a grey solid product. NMR analysisshowed the product to have a structure consistent with3,3-bis(4-methoxyphenyl)-6-methoxy-7-morpholino-11-(2-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 11

Step 1

Into a 1 L reaction flask containing acetic anhydride (600 mL) was added7,7-dimethyl-7H-benzo[c]fluoren-5-ol (150 g) followed by the additionof, 4-dimethylaminopyridine (DMAP) (0.2 g). The reaction mixture washeated to 130° C. and maintained at this temperature for 2 to 3 hours.The resulting reaction mixture was cooled to 120° C. and maintained atthis temperature overnight and then cooled to room temperature prior tobeing poured into ice water and stirred for 2 hours. An off-white solidformed and was collected by filtration. The recovered solid was washedwith water, and then with MeOH/water (v/v, 50/50). The product wasair-dried to yield 175 g solid and was used in the next step withoutfurther purification.

Step 2

Into a 1 L reaction flask containing 400 mL of DMF was added the productof Step 1 (120 g) followed by the addition of N-bromosuccinimide (NBS)(82 g). The reaction mixture was heated to 90° C., spiked to 120° C.briefly and returned to about 95° C. and was heated at this temperaturefor 4 hours. Additional NBS was added (8 g) and the reaction mixture washeated for 2 more hours. The resulting reaction mixture was poured intowater and was extracted with EtOAc. The recovered organic layer waswashed with water (3×200 mL), dried over MgSO₄ and concentrated undervacuum to provide product. The product was slurried in methanol and thesolid was recovered by filtration, washed with methanol (3×200 mL) anddried to provide a light yellowish solid (107 g). The product was usedin the next step without purification.

Step 3

Into a 1 L reaction flask containing MeOH (500 mL) was added the productof Step 2 (107 g) followed by the addition of conc. HCl, 37% (3 g). Thereaction mixture was heated to reflux for 2 hours. The solvents wereremoved from the resulting reaction mixture to yield about 100 g solid.The recovered solid was slurried in about 250 mL dichloromethane(DCM)/Hexanes (v/v, 50/50) for 10 minutes at room temperature. Theslurry was filtered and the recovered solid was washed with DCM/Hexanes(v/v, 5/5) to provide about 47 g of product. NMR analysis showed theproduct to have a structure consistent with7,7-dimethyl-9-bromo-7H-benzo[c]fluoren-5-ol.

Step 4

The product of Step 3 (20 g) and 4-trifluoromethyl phenyl boronic acid(15.8 g) were added to a 1 L reaction flask containing a solution ofdimethoxyethane (200 mL) and water (100 mL) followed by the addition ofNa₂CO₃ (12.5 g). The resulting solution was bubbled with nitrogen for 10minutes and then the palladium catalyst, Pd[PPh3]4, (3 g) was added tothe reaction mixture. The reaction mixture was heated to refluxtemperatures under a nitrogen atmosphere. The initially light greenishwhite solution turned dark upon heating. After 1 hour, the reactionmixture was cooled to room temperature and poured into 400 mL of waterfollowed by extraction with ethyl acetate (2×300 mL). The organic layerswere combined and washed with saturated NaCl solution (1×400 mL). Thisorganic layer was dried over anhydrous sodium sulfate and concentratedby rotary evaporation to yield the product (23 g) which was used in thenext step without purification.

Step 5

The product of Step 4 (4.0 g),1-phenyl-1-(4-morpholinophenyl)-2-propyn-1-ol (3.47 g, 1.2 equivalents)and chloroform (120 mL) were combined in a 500 mL reaction flask. Tothis was added PPTS (0.25 g, 0.1 equivalents) and the reaction mixturewas heated to 50° C. and maintained at this temperature for 4 hours.Added 1-phenyl-1-(4-morpholinophenyl)-2-propyn-1-ol (0.75 g) and heatedthe reaction mixture for another 1 hour. The reaction mixture was thenwashed with 400 mL of a 1:1 mixture of saturated aqueous NaHCO₃ andwater. The organic layer was dried over anhydrous sodium sulfate andconcentrated by rotary evaporation. The resulting residue was purifiedby column chromatography using a mixture of 60% hexane, 35% methylenechloride and 5% ethyl acetate as the starting eluant. The purplefractions were combined and rotovaped to obtain 4.6 grams of purplefoam. NMR analysis show the purple product to have a structureconsistent with3-phenyl-3′-(4-morpholinophenyl)-11-(4-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 12

Step 1

The product of Step 3 of Example 11,7,7-dimethyl-9-bromo-7H-benzo[C]fluoren-5-ol (15 g) and2-trifluoromethyl phenyl boronic acid (10.5 g) were added to a solutionof dimethoxyethane (150 mL) and water (75 mL) in a 1 L reaction flask,followed by addition of Na₂CO₃ (9.4 g). The resulting solution wasbubbled with nitrogen for 10 minutes and a palladium catalyst,Pd[PPh3]4, (2.5 g) was added to the reaction mixture. The resultingreaction mixture was heated to reflux temperature under a nitrogenatmosphere. The initially light greenish white solution turned dark uponheating. After refluxing overnight, the reaction was cooled to roomtemperature and poured into 400 mL of water followed by extraction withethyl acetate (2×300 mL). The organic layers were recovered, combinedand washed with saturated NaCl solution (1×400 mL). The resultingorganic layer was dried over anhydrous sodium sulfate and concentratedby rotary evaporation to yield the product (17.2 g). This material wasnot purified further and used in the next step.

Step 2

The product of Step 1 (3.0 g),1-phenyl)-1-(4-morpholinophenyl)-2-propyn-1-ol (2.50 g, 1.15equivalents) and dichloroethane (120 mL) were combined in a 500 mLreaction flask. To this mixture was added PPTS (0.56 g, 0.3 equivalents)and trimethyl orthoformate (1.6 g, 2 equivalents). The reaction mixturewas heated to reflux and maintained at that temperature for 2 hours. Thefollowing materials were added to the reaction mixture:1-phenyl)-1-(4-morpholinophenyl)-2-propyn-1-ol (1.0 g), PPTS (0.2 gramsof and 0.5 grams of trimethyl orthoformate and it was again to refluxtemperature for another 2 hours. The reaction mixture was cooled to roomtemperature and washed with 100 mL of a 1:1 mixture of saturated aqueousNaHCO₃ and water. The organic layer was dried over anhydrous sodiumsulfate and concentrated by rotary evaporation. The resulting residuewas purified using 20% ethyl acetate/80% hexanes (v/v) by chromatographyto obtain 4.4 grams of a blue solid. Precipitation from diethyl etheryielded a white solid. The pure product was filtered, washed withdiethyl ether and then dried under vacuum to obtain 2.80 grams of abluish white solid. NMR analysis showed the product to have a structureconsistent with3-(4-morpholinophenyl)-3-phenyl-11-(2-trifluoromethyl)phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 13

Step 1

Into a suitable reaction flask was added2,3-dimethoxy-7,7-dimethyl-9-bromo-7H-benzo[C]fluoren-5-ol (6.5 g),4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.4 g), potassium acetate (6.9g) and a palladium catalyst, Pd(dppf)Cl₂, (0.75 g) in dry triethylamine(100 mL). The solution was purged with nitrogen for 10 minutes and thenstirred at 80° C. overnight. The solvent was removed and the resultingresidue was extracted with ethyl acetate and water. The recoveredorganic phase was dried with sodium sulfate and subject to columnchromatography using 30% ethyl acetate/hexanes as eluant to provide 7.25grams of product. NMR analysis showed the product to have a structureconsistent with2,3-dimethoxy-7,7-dimethyl-9-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-7H-benzo[C]fluoren-5-ol.

Step 2

The product of Step 1 (1.0 g), 2-bromo-3-(trifluoromethyl)pyridine (0.5g), potassium carbonate (0.5 g), palladium acetate (0.04 g),triphenylphosphine (0.1 g), 1,2-dimethoxyethane (40 mL), and water (20mL) were combined in a 200 mL reaction flask. Nitrogen was bubbledthrough the reaction mixture for 10 minutes. The solution was stirred at80° C. overnight. The resulting reaction mixture was cooled to roomtemperature and the aqueous phase separated. The recovered organic phasewas diluted with dichloromethane and washed twice with brine beforedrying over Na₂SO₄ and evaporating the solvent. The resulting residuewas chromatographed on a short silica gel column, eluting with 30% EtOAcin hexanes to provide 0.4 g of product. This solid was used as is forthe next reaction.

Step 3

The product of Step 2 (0.14 g), 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol(0.12 g) and chloroform (15 mL) were combined in a 50 mL reaction flask.To this mixture, PPTS was added (0.05 g). The reaction mixture wasstirred at room temperature overnight. The solvent was removed beforepurifying the residue by column chromatography on silica gel. Productcontaining fractions were combined and the product was recrystallizedfrom dichloromethane/ethanol mixture to provide 0.17 g of product asyellow crystals. NMR analysis showed the product to have a structureconsistent with3-(4-butoxyphenyl)-3-(4-methoxyphenyl)-6,7-dimethoxy-11-(3-(trifluoromethyl)pyridin-2-yl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 1

2,3-Dimethoxy-7,7-dimethyl-9-phenyl-7H-benzo[C]fluoren-5-ol (10 g) wasadded to chloroform (200 mL) in a 500 mL reaction flask followed by theaddition of PPTS (0.6 g) and 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol (7.1g). After two hours of stirring at room temperature, PPTS (0.6 g) wasadded. After an additional 30 minutes of stirring,1,1-bis(4-methoxyphenyl)-2-propyn-1-ol (1.2 g) was added. After hour ofstirring, 1,1-bis(4-methoxyphenyl)-2-propyn-1-ol (1.5 g) was added. Theresulting reaction mixture was stirred for 2 hours at room temperatureand PPTS (0.6 g) was added. After about 16 hours, a saturated aqueoussolution of NaHCO₃ (80 mL) was added. The layers separated and theorganic layer was recovered. The aqueous layer was extracted withdichloromethane (2 times, 50 mL each time). The organic layers werecombined, dried over anhydrous MgSO₄, and concentrated under vacuum toyield unpurified product (30 g). The product was slurried overacetone/diethyl ether (Et₂O) (55 mL, 25/75, volume ratio). The recoveredsolid was isolated and washed with acetone/Et₂O (25175, volume ratio, 2times, 15 mL each time). About 9 g product was recovered. NMR analysisshowed the product to have a structure consistent with3,3-bis(4-methoxyphenyl)-6,7-dimethoxy-11-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 2

3,3-Di(4-methoxyphenyl)-6,7-dimethoxy-11-(4-fluorophenyl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyranwas prepared by the procedure of Example 5 of U.S. Patent Publication2006-0228557.

Comparative Example 3

3,3-Di(4-methoxyphenyl)-10,11-dimethoxy-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyranwas prepared by the procedure of Example 4 of U.S. Pat. No. 6,296,785.

Comparative Example 4

Piperidine (2.4 g) was dissolved in dTHF (150 mL) in a 500 mL reactionflask. BuLi (11.2 mL, 2.5 M in hexanes) was added slowly. The resultingsolution was stirred at room temperature for 30 minutes and3-(4-morpholinophenyl)-3-(4-methoxyphenyl)-6,7-dimethoxy-11-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4-]naphtho[1,2-b]pyran(9.0 g) was added slowly to the reaction mixture. After 1.5 h stirringat room temperature, more BuLi (5 mL) was added. The reaction wasexothermic and temperature went up to 24° C. from 21° C. The reactionwas stirred for two more hours and poured into a brine solution. Thelayers separated and the organic layer was collected. The aqueous layerwas extracted with dichloromethane (2 times, 30 mL each time). Theorganic layers were combined, dried over anhydrous MgSO₄, andconcentrated under vacuum to yield unpurified product (9.5 g). Theproduct was purified by column chromatography (EtOAc/Hexanes, 3/2,volume ratio) to yield product 7 g. NMR analysis showed the product tohave a structure consistent with3,3-bis(4-methoxyphenyl)-6-methoxy-7-piperidino-11-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 5

2,3-Dimethoxy-7,7-dimethyl-9-phenyl-7H-benzo[C]fluoren-5-ol, 10 g wasadded to dichloromethane (200 mL) in a 500 mL reaction flask followed bythe addition of PPTS (0.6 g) and1-(4-methoxyphenyl)-1-(4-morpholinophenyl)-2-propyn-1-ol (8.6 g). Afterone hour of stirring at room temperature, PPTS (0.6 g) was added. Thereaction mixture was stirred at room temperature for about 60 hours anda saturated aqueous solution of NaHCO₃ (80 mL) was added. The layersseparated and the organic layer was recovered. The aqueous layer wasextracted with dichloromethane (2 times, 50 mL each time). The organiclayers were combined, dried over anhydrous MgSO₄, and concentrated undervacuum to yield unpurified product (23 g). The product was slurried overacetone/Et₂O/hexanes (100 mL, 10/10/90, volume ratio). The resultingsolid was isolated and washed with acetone/hexane (10/90, volume ratio,2 times, 50 mL each time) to yield about 16.7 g product. NMR analysisshowed the product to have a structure consistent with3-(4-morpholinophenyl)-3-(4-methoxyphenyl)-6,7-dimethoxy-11-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 6

Step 1

Piperidine (11.6 grams, 2.7 eq.) was weighed into a 500 mL dry reactionflask. dTHF (150 mL) was added to the reaction flask and stirred under anitrogen atmosphere at room temperature. BuLi (50.5 mL (2.5 eq.) of 2.5M in hexanes) was added dropwise to the reaction mixture over a 5-minuteperiod. The reaction mixture became warm and a little cloudy.2,3-Dimethoxy-7,7-dimethyl-9-phenyl-7H-benzo[C]fluoren-5-ol (20.0 g) wasadded in portions over a 10-minute period to the reaction mixture. Theresulting solution was stirred at 40° C. for 2 hours. Piperidine (1.2 g)and then 5 mL of BuLi (2.5 M in hexanes) was added dropwise to thereaction mixture over a 5-minute period. The resulting solution wasstirred at 40° C. for another 2 hours. After cooling to roomtemperature, the reaction mixture was poured into 400 mL of saturatedNaCl solution and neutralized carefully with 10% HCl until pH˜=7.Extraction was done with two 250 mL portions of EtOAc. The organiclayers were combined and washed with saturated NaCl solution (1×400 mL)followed by drying over anhydrous sodium sulfate. The solvent wasremoved by rotary evaporation to yield an off white solid. This materialwas purified by slurrying in diethyl ether. The resulting product wasfiltered off and dried under vacuum to yield 17.7 grams of the primaryproduct,2-piperidino-3-dimethoxy-7,7-dimethyl-9-phenyl-7H-benzo[C]fluoren-5-oland (3.95 grams) of a secondary product.

Step 2

The primary product of Step 1 (20.0 g) was weighed into a 500 mLreaction flask and toluene (154 mL) was added. DBSA (0.73 g, 0.05equivalents) was added. The reaction mixture was heated to 75° C. andstirred under a nitrogen atmosphere. A solution of1-(4-methoxyphenyl)-1-(4-morpholinophenyl)-2-propyn-1-ol (17.26 g, 1.2eq.) in toluene (77 mL) was added drop wise to the reaction flask over a1 hour period. The reaction mixture was stirred at 75° C. After 4 hours,1-(4-methoxyphenyl)-1-(4-morpholinophenyl)-2-propyn-1-ol (5 g) was addedand the resulting mixture was stirred at 75° C. After about 16 hours,1-(4-methoxyphenyl)-1-(4-morpholinophenyl)-2-propyn-1-ol (2.5 g) andPPTS (0.5 g) were added and the reaction mixture was heated for another4 hours. The reaction mixture was cooled to room temperature, dilutedwith 250 mL of EtOAc, and washed with 400 mL of a 1:1 mixture ofsaturated aqueous NaHCO₃ and water. The layers separated and therecovered organic layer was dried over anhydrous sodium sulfate andconcentrated by rotary evaporation. The resulting material was purifiedby column chromatography (50% hexanes, 40% methylene chloride and 10%EtOAc as the starting eluant) and the photochromic fractions werecombined, concentrated by rotary evaporation, and dried under vacuum toyield 21 grams of purplish foam. This foam was further purified bycrystallization from diethyl ether to obtain an off white solid. NMRanalysis show the product to have a structure consistent with3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-6-dimethoxy-7-piperidino-11-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 7

Morpholine (3.5 g) was dissolved in dTHF (80 mL) in a 250 mL reactionflask. BuLi (1.6 M in hexanes, 10 mL) was added slowly. The resultedsolution was stirred at room temperature for 30 minutes and the productofCE-5,3-(4-morpholinophenyl)-3-(4-methoxyphenyl)-6,7-dimethoxy-11-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran(3.5 g) was added slowly to the reaction mixture. The reaction wasgently warmed for one hour. The resulting reaction mixture was cooled toroom temperature and poured into a brine solution. The layers wereseparated and the organic layer was collected. The aqueous layer wasextracted with dichloromethane (2 times, 30 mL each time). The organiclayers were combined, dried over anhydrous MgSO₄, concentrated undervacuum and purified by column chromatography (EtOAc/Hexanes, 3/2, volumeratio) to give product 1.3 g. NMR analysis show the product to have astructure consistent with3,3-bis(4-methoxyphenyl)-6,7-dimethoxy-11-(2-trifluoromethylphenyl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 8

2,3-Dimethoxy-7,7-dimethyl-9-phenyl-7H-benzo[C]fluoren-5-ol (1.7 g) and1,1-bis[4-((ditetrahydro-2H-pyran-2-yl)oxy)phenyl]-2-propyn-1-ol (2.15g) were added to dichloromethane (200 mL) in a 500 mL flask followed bythe addition of PPTS (60 mg) to the reaction mixture. The resultingsolution was stirred at room temperature. After about 16 hours, MeOH (10mL) and PPTS (60 mg) were added to the reaction mixture. The product wasinsoluble and isolated by filtration and treated with PPTS (0.2 g) inethanol/acetone (1/5, volume ratio) at room temperature for about 64hours. The resulting off-white solid product (0.83 g) was isolated. NMRanalysis show the product to have a structure consistent with3,3-bis(4-hydroxyphenyl)-6,7-dimethoxy-11-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 9

STEP 1

A solution of morpholine (27.8 mL) in dTHF (600 mL) was added to a 2 Lreaction flask under nitrogen. Methyl lithium (1.4 M in diethyl ether,223 mL) was added over 20 minutes at 0° C. The resulting mixture wasstirred for 30 mins at 0° C. and then warmed to room temperature andstirred for 20 min. A solution of2,3-dimethoxy-7,7-dimethyl-7H-benzo[C]fluoren-5-ol (20 g) in dTHF (300mL) was added to the reaction mixture over an interval of 30 minutes.The resulting reaction was heated to reflux. After heating for 1.5 hoursat reflux, the reaction was cooled to room temperature and stirred forabout 16 hours. The resulting reaction mixture was poured to ice waterand the layers were separated. The aqueous layer was extracted withEtOAc (4 times with 100 mL each time). The combined organic layers weredried over anhydrous MgSO₄ and concentrated to yield a dark brown oil.The dark oil was crystallized from a mixture of Hexanes/EtOAc (3:1,volume ratio) to yield 17.9 g of a powder. NMR analysis showed theproduct to have a structure consistent with2-morpholino-3-methoxy-7,7-dimethyl-7H-benzo[C]fluoren-5-ol.

Step 2

The product of Step 1 (5 g) was added to dichloromethane (100 mL) in a250 mL reaction flask, followed by addition of1,1-bis(4-methoxyphenyl)-2-propyn-1-ol (2 g). The reaction was stirredat room temperature for 16 hours and then poured into a 5 weight percentaqueous solution of NaHCO₃. The layers separated and the resultingorganic layer was recovered and the aqueous layer was extracted withdichloromethane (2 times with 20 mL each time). The organic layers werecombined, dried over anhydrous MgSO₄ and concentrated to provide 6.3 gof product. The product was purified by column chromatography[EtOAc/Hexanes, 1/3, volume ratio] to provide 2.4 g of product. NMRanalysis showed the product to have a structure consistent with3,3-bis(4-methoxyphenyl)-6-methoxy-7-morpholino-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Comparative Example 10

The product of Step 3 of Example 11,7,7-dimethyl-9-phenyl-7H-benzo[C]fluoren-5-ol (2.0 g) was dissolved inchloroform (125 mL) in a 500 mL reaction flask. To this was addedp-toluene sulfonic acid (PTSA) (0.2 g). The reaction was stirred at 50°C. under nitrogen. Over a 30 minute interval, portions of1-phenyl-1-(4-morpholinophenyl)-2-propyn-1-ol (1.74 g) were added to thereaction mixture. The resulting reaction mixture was stirred at 50° C.for 2 hours. The reaction mixture was cooled to room temperature, washedwith 100 mL of a saturated aqueous NaHCO₃ solution, and extracted withchloroform. The recovered organic layers were combined, dried over MgSO4and concentrated under vacuum. The product was purified bychromatography to yield 1.6 grams of a product that was treated withdiethyl ether to yield an off-white solid (1.2 g). NMR analysis showedthe product to have a structure consistent with3-(4-phenyl)-3′-(4-morpholinophenyl)-11-phenyl-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Part 2: Photochromic Performance Testing

The photochromic performance of the photochromic materials of Examples1-13 and Comparative Examples (CE) 1-10 were tested as follows. Aquantity of the photochromic material to be tested, calculated to yielda 1.5×10⁻³ M solution, was added to a flask containing 50 grams of amonomer blend of 4 parts ethoxylated bisphenol A dimethacrylate (BPA 2EODMA), 1 part poly(ethylene glycol) 600 dimethacrylate, and 0.033 weightpercent 2,2′-azobis(2-methyl propionitrile) (AIBN). The photochromicmaterial was dissolved into the monomer blend by stirring and gentleheating. After a clear solution was obtained, it was vacuum degassedbefore being poured into a flat sheet mold having the interiordimensions of 2.2 mm×6 inches (15.24 cm)×6 inches (15.24 cm). The moldwas sealed and placed in a horizontal air flow, programmable ovenprogrammed to increase the temperature from 40° C. to 95° C. over a 5hour interval, hold the temperature at 95° C. for 3 hours and then lowerit to 60° C. for at least 2 hours. After the mold was opened, thepolymer sheet was cut using a utility knife to score the surface andsnap into 2 inch (5.1 cm) test squares.

The photochromic test squares prepared as described above were testedfor photochromic response on an optical bench. Prior to testing on theoptical bench, the photochromic test squares were exposed to 365 nmultraviolet light for about 15 minutes to cause the photochromicmaterial to transform from the ground state-form to an activated-stateform, and then placed in a 75° C. oven for about 15 minutes to allow thephotochromic material to revert back to the ground state-form. The testsquares were then cooled to room temperature, exposed to fluorescentroom lighting for at least 2 hours, and then kept covered (that is, in adark environment) for at least 2 hours prior to testing on an opticalbench maintained at 73° F. (23° C.). The bench was fitted with a300-watt xenon arc lamp, a remote controlled shutter, a Melles Griot KG2filter that modifies the UV and IR wavelengths and acts as a heat-sink,neutral density filter(s) and a sample holder, situated within a waterbath, in which the square to be tested was inserted. A collimated beamof light from a tungsten lamp was passed through the square at a smallangle (approximately) 30° normal to the square. After passing throughthe square, the light from the tungsten lamp was directed to acollection sphere, where the light was blended, and on to an OceanOptics S2000 spectrometer where the spectrum of the measuring beam wascollected and analyzed. The λ_(max-vis) is the wavelength in the visiblespectrum at which the maximum absorption of the activated-state form ofthe photochromic compound in a test square occurs. The λ_(max-vis)wavelength was determined by testing the photochromic test squares in aVarian Cary 300 UV-Visible spectrophotometer; it may also be calculatedfrom the spectrum obtained by the S2000 spectrometer on the opticalbench.

The saturated optical density (“Sat'd OD”) for each test square wasdetermined by opening the shutter from the xenon lamp and measuring thetransmittance after exposing the test chip to 3 W/m2 UVA radiation for30 minutes. The λ_(max-vis) at the Sat'd OD was calculated from theactivated data measured by the S2000 spectrometer on the optical bench.The First Fade Half Life (“T_(1/2)”) or Bleach Rate is the time intervalin seconds for the absorbance of the activated-state form of thephotochromic material in the test squares to reach one half the Sat'd ODabsorbance value at room temperature (23° C.), after removal of thesource of activating light.

Part 3: Test Results

Results for the photochromic materials tested are listed below in Table1.

TABLE 1 Photochromic Test Data λ_(max) (nm) Bleach Rate Example VisibleSat. OD T_(1/2) (sec) 1 448 1.25 163 2 458 0.91 171 3 456 0.93 134 13 457 1.06 184 CE 1 453 1.15 243 CE 2 452 1.09 238 CE 3 451 1.27 236 4 4821.59 276 CE 4 482 1.99 338 5 481 0.54 148 CE 5 479 0.68 197 6 507 1.08232 CE 6 504 1.41 299 7 499 0.93 191 CE 7 497 0.91 249 8 460 0.84 114 CE8 459 0.94 155 9 474 1.36 242 10  473 1.65 248 CE 9 471 1.68 348 11  5921.21 182 12  587 1.27 200  CE 10 592 1.36 248

Examples 1, 2 and 3 have the trifluoromethyl substituent(s) located atthe 4-position, 3- and 5-positions and the 2-position of the phenyl atthe 11-position of each compound, respectively. Example 13 has atrifluoromethyl substituent located at the 3-position of the pyridylring at the 11-position of the compound. This example also has a butoxysubstituted phenyl at the 3 position which is expected to have verylittle, if any effect on the Bleach (T1/2) when compared to a methoxysubstituted phenyl at the same position. Comparative Example (CE) 1 hasan unsubstituted phenyl at the 11-position, CE-2 has a 4-fluorophenyl atthe 11-position and CE-3 is unsubstituted at the 11-position. Examples4-7 each have the trifluoromethyl located at the 4-position of thephenyl at the 11-position and CE-4-7 have an unsubstituted phenyl at the11-position on each corresponding comparative example. Example 8 hastrifluoromethyl groups located at the 3- and 5-positions and CE-8 has anunsubstituted phenyl at the 11-position. Example 9 has thetrifluoromethyl at the 4-position and Example 10 has the trifluoromethylat the 2-position of the phenyl at the 11-position. CE-9 isunsubstituted at the 11-position. Examples 11 and 12 have thetrifluoromethyl substituent(s) located at the 4-position and the2-position of the phenyl at the 11-position of each compound,respectively, and the 6- and 7-positions are unsubstituted. CE-10 has anunsubstituted phenyl at the 11-position and is also unsubstituted at the6- and 7-positions. In each comparison, Examples 1-13 demonstrated afaster bleach rate (T1/2) than the corresponding Comparative Examples1-10

Whereas particular embodiments of this invention have been describedabove for purposes of illustration, it will be evident to those skilledin the art that numerous variations of the details of the presentinvention may be made without departing from the invention as defined inthe appended claims.

What is claimed is:
 1. A photochromic material comprising an indeno-fused naphthopyran having the following general structural formula (I) or (II):

the photochromic material having a pi-conjugation extending group bonded to the 11-position of said indeno-fused naphthopyran, said pi-conjugation extending group having at least one pendent halo-substituted group bonded thereto, said pi-conjugation extending group extending the pi-conjugation system of said indeno-fused naphthopyran, wherein the 13-position of said indeno-fused naphthopyran is substantially free of spiro-substituents.
 2. The photochromic material of claim 1 wherein said pi-conjugation extending group is a group represented by —C(R₃₀)═C(R₃₁)(R₃₂) or —C≡C—R₃₃, wherein R₃₀, R₃₁ and R₃₂ are each independently, amino, dialkyl amino, diaryl amino, acyloxy, acylamino, a substituted or unsubstituted C₁-C₂₀ alkyl, a substituted or unsubstituted C₂-C₂₀ alkenyl, a substituted or unsubstituted C₂-C₂₀ alkynyl, halogen, hydrogen, hydroxy, oxygen, a polyol residue, a substituted or unsubstituted phenoxy, a substituted or unsubstituted benzyloxy, a substituted or unsubstituted alkoxy, a substituted or unsubstituted oxyalkoxy, alkylamino, mercapto, alkylthio, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclic group, provided that at least one of R₃₀, R₃₁ and R₃₂ is said pendent halo-substituted group, and R₃₃ is said pendent halo-substituted group.
 3. The photochromic material of claim 1 wherein said pi-conjugation extending group is selected from: a substituted or unsubstituted aryl; and a substituted or unsubstituted heteroaryl.
 4. The photochromic material of claim 3 wherein said pi-conjugation extending group bonded to the 11-position of said indeno-fused naphthopyran is selected from substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, wherein said substituted aryl and said substituted heteroaryl are in each case independently substituted with at least one member selected from substituted or unsubstituted alkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted oxyalkoxy, amide, substituted or unsubstituted amino, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, azide, carbonyl, carboxy, ester, ether, halogen, hydroxy, polyol residue, substituted or unsubstituted phenoxy, substituted or unsubstituted benzyloxy, cyano, nitro, sulfonyl, thiol, and substituted or unsubstituted heterocyclic group, provided that if the aryl group or the heteroaryl group comprises more than one substituent, each substituent may be independently chosen.
 5. The photochromic material of claim 1 wherein said pendent halo-substituted group of said pi-conjugation extending group is selected from halo-substituted(C₁-C₁₀)alkyl, halo-substituted(C₂-C₁₀)alkenyl, halo-substituted(C₂-C₁₀)alkynyl, halo-substituted(C₁-C₁₀)alkoxy and halo-substituted(C₃-C₁₀)cycloalkyl, and wherein each halo group of each pendent halo-substituted group being independently selected from fluorine, chlorine, bromine and iodine.
 6. The photochromic material of claim 1 wherein said photochromic material displays hyperchromic absorption of electromagnetic radiation having a wavelength from 320 nm to 420 nm as compared to a comparative photochromic material comprising a comparable indeno-fused naphthopyran that is substantially free of said pi-conjugation extending group bonded to the 11-position of said comparable indeno-fused naphthopyran.
 7. A photochromic article comprising a substrate and a photochromic material according to claim 1 connected to at least a portion of the substrate.
 8. The photochromic article of claim 7 wherein the photochromic article is an optical element, said optical element being at least one of an ophthalmic element, a display element, a window, a mirror and a liquid crystal cell element.
 9. The photochromic article of claim 8 wherein the optical element is an ophthalmic element, said ophthalmic element being at least one of a corrective lens, a non-corrective lens, a magnifying lens, a protective lens, a visor, goggles and a lens for an optical instrument.
 10. The photochromic article of claim 7 wherein the substrate comprises a polymeric material and the photochromic material is incorporated into at least a portion of the polymeric material.
 11. The photochromic article of claim 10 wherein the photochromic material is at least one of blended with at least a portion of the polymeric material, bonded to at least a portion of the polymeric material, and imbibed into at least a portion of the polymeric material. 